Amines catalysis

Abstract

Process of making amines by inter alia the (i) intramolecular condensation of an amino compound to an amine having a lower molecular weight or (ii) the intermolecular condensation of an amino compound with one or more of another amino compound or a compound containing an alcoholic hydroxyl group using a Group IVB metal oxide condensation catalyst. The preferred process involves the manufacture of alkyleneamines, most desirably polyalkylenepolyamines, by such condensation reactions utilizing catalysts containing titanium oxide, zirconium oxide or mixtures of them.

Description

The following are related, commonly assigned applications, filed on an even date herewith: U.S. patent application Ser. No. 390,714; U.S. patent application Ser. No. 390,709 now U.S. Pat. No. 4,983,736 U.S patent application Ser. No. 390,706; U.S. patent application Ser. No. 390,828 now U.S. Pat. No. 5,101,074 and U.S. patent application Ser. No. 390,708 now abandoned; all incorporated herein by reference.

BRIEF SUMMARY OF THE INVENTION

1. Technical Field

A process of making amines which comprises condensing an amino compound in the presence of a Group IVB metal oxide condensation catalyst.

A catalyst composition comprising a high surface area Group IVB metal oxide condensation catalyst containing one or more performance modifiers.

2. Background of the Invention

There is a substantial body of literature directed to the use of acid catalysts to effect intramolecular and intermolecular condensation of amino compounds. U.S. Pat. No. 2,073,671 and U.S. Pat. No. 2,467,205 constitute early prior work on the use of acid condensation catalysts to condense amino compounds. U.S. Pat. No. 2,073,671 discusses, in a general fashion, the catalytic intermolecular condensation of alcohols and amines or ammonia using the same phosphate catalysts later favored by U.S. Pat. No. 2,467,205 for the intramolecular condensation of amines. The two patents are not in harmony over the use of other materials as catalysts. To illustrate this point, U.S. Pat. No. 2,073,671 states:

"Alumina, thoria, blue oxide of tungsten, titania, chromic oxide, blue oxide of molybdenum and zirconia have been mentioned in the literature for use as catalysts in carrying out these reactions but their effectiveness is so low that no practical application has been made of their use." whereas U.S. Pat. No. 2,467,205 in describing the self-condensation of ethylenediamine (EDA) under vapor phase conditions, to initially produce ethyleneamines, but after recycle, eventually generates piperazine through multistep condensation reactions, followed by deamination, recommends "dehydration catalysts" which are thereafter characterized as "silica gel, titania gel, alumina, thoria, boron phosphate, aluminum phosphate, and the like."

U.S. Pat. No. 2,073,671 describes the condensation catalyst in the following terms:

". . . a heated catalyst or contact mass containing phosphorus and especially one or more of the oxygen acids of phosphorus, their anhydrides, their polymers, and their salts; for example, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous pentoxide, dimetaphosphoric acid, trimetaphosphoric acid primary ammonium phosphate, secondary ammonium phosphate, normal ammonium phosphate, ammonium metaphosphate, secondary ammonium pyrophosphate, normal ammonium pyrophosphate, aluminum phosphate, aluminum acid phosphate and mixtures of two or more of such materials." whereas U.S. Pat. No. 2,467,205 describes one of the preferred catalysts as "basic aluminum phosphate".

U.S. Pat. No. 2,454,404 effects the "catalytic deamination of alkylene polyamines" by reacting diethylenetriamine (DETA) vapor over solid catalysts such as activated alumina, bauxite, certain aluminum silicates such as kaolin and oxides of thorium, titanium and zirconium.

U.S. Pat. Nos. 2,073,671 and 2,467,205 demonstrate a common experience in using aluminum phosphate as a condensation catalyst to produce aliphatic amines, and U.S. Pat. Nos. 2,454,404 and 2,467,205 contemplate the other solid catalysts for deamination of amines to make heterocyclic noncyclic amines. In general, the reaction conditions under which deamination to effect cyclization occurs are more severe than those employed for condensation to generate noncyclic molecules, all other factors being comparable.

It is suffice to state that neither of U.S. Pat. Nos. 2,467,205 and 2,454,404 show the actual use of oxides of Group IVB metals as catalysts for any purpose nor do they indicate the nature of these oxides in terms of properties in order to distinguish one oxide of the class form another. U.S. Pat. No. 2,073,671 suggests that the oxides of Group IVB metals would be ineffectual condensation catalysts.

U.S. Pat. Nos. 4,540,822, 4,584,406, and 4,588,842 depict the use of Group IVB metal oxides as supports for phosphorus catalysts used to effect the condensation of amino compounds with alkanolamines. They each show that the Group IVB metal oxide per se is essentially inactive as a catalyst. In other words, these patents specifically tested certain Group IVB metal oxides as condensation catalysts and found they were inert, i.e., they failed to affect the reactants or cause any condensation. U.S. Pat. No. 4,540,822 at Table I states that catalyst "5494-4" is titania (TiO.sub.2) and at col. 9, lines 49-52, the patentee finds that titania is "essentially inert", see Table II. In Table IV, the patentee shows that the calcined phosphoric treated titania contained a small amount of sulfur impurity. Table VI is an analysis of the titania pellet and shows no detected sulfur. This can be interpreted as indicating that the sulfur impurity detected was associated with the phosphoric acid. U.S. Pat. No. 4,584,406 demonstrates that zirconia (No. "5484-37") is also inactive as a condensation catalyst, see Table II therein. The same data ca be found in U.S. Pat. No. 4,588,842.

U.S. Pat. No. 683,335 describes the use of tungstophosphoric acid, molybdophosphoric acid or mixtures deposited on titania as catalysts for the condensation of amines and alkanolamines to make polyalkylenepolyamines. Examples 2-7 characterize titania surface areas of 51, 60 and 120 m.sup.2 /gm. There is no description in the patent dealing with the use of the tiania support as a catalyst.

The only reasonable conclusion to be drawn from the above prior art is that titania is a favorable catalyst support material for the condensation of amines and has no catalytic activity for effecting condensation of amines.

U.S. Pat. Nos. 4,314,083, 4,316,840, 4,362,886 and 4,394,524 disclose the use of certain metal sulfates as useful catalysts for the condensation of alkanolamine and an amino compound. No distinction is made between the sulfur compounds in respect to catalytic efficacy. Sulfuric acid is as good as any metal sulfate, and all metal sulfates are treated as equivalents. At column 8 of U.S. Pat. No. 4,314,083, it is noted that boron sulfate "gave extremely high selectivity at a low level" of EDA. However, selectivity in general was shown to increase with an increase of EDA relative to MEA in the feed. The only specific metal sulfates disclosed in the patents are antimony sulfate, beryllium sulfate, iron sulfate and aluminum sulfate. No Group IVB metal oxide containing residual sulfur is described by these patents.

In the typical case of the manufacture of alkyleneamines, mixtures with other alkyleneamines (including a variety of polyalkylenepolyamines and cyclic alkylenepolyamines) are formed. The same holds true when the object of the process is to produce polyalkylenepolyamines whether acyclic or cyclic, in that a variety of amino compounds are also formed. Each of these cyclic and acyclic alkyleneamines can be isolated from the mixture.

The acid catalyzed condensation reaction involving the reaction of an alkanolamine with an amino compound in the presence of an acidic catalyst is believed to proceed through the mechanism of esterifying free surface hydroxyl groups on the acid catalyst with the alkanolamine and/or by protonating the alkanolamine in the presence of the acid catalyst, followed by loss of water and amine condensation of the ester or the hydrated species, as the case may be, to form the alkyleneamine. Illustrative prior art directed primarily to the cyclic polyalkylenepolyamines (heterocyclic polyamines), but not necessarily limited to the aforementioned acid condensation reaction, are: U.S. Pat. Nos. 2,937,176, 2,977,363, 2,977,364, 2,985,658, 3,056,788, 3,231,573, 3,167,555, 3,242,183, 3,297,701, 3,172,891, 3,369,019, 3,342,820, 3,956,329, 4,017,494, 4,092,316, 4,182,864, 4,405,784 and 4,514,567; European Pat. Applications 0 069 322, 0 111 928 and 0 158 319; East German Pat. No. 206,896; Japanese Pat. Publication No. 51-141895; and French Pat. No. 1,381,243. The evolution of the art to the use of the acid catalyzed condensation reaction to generate acyclic alkyleneamines, particular acyclic polyalkylenepolyamines, as the predominant products stemmed from the initial disclosure in U.S. Pat. No. 4,036,881, patented Jul. 19, 1977, though earlier patent literature fairly well characterized such an effect without labeling it so, see U.S. Pat. No. 2,467,205, supra. The acid catalysts are phosphorus compounds and the reaction is carried out in the liquid phase. The trend in this catalyst direction was early set as demonstrated by U.S. Pat. Nos. 2,073,671 and 2,467,205, supra. A modification of this route includes the addition of ammonia to the reaction, see, for example, U.S. Pat. No. 4,394,524, patented Jul. 19, 1983, and U.S. Pat. No. 4,463,193, patented Jul. 31, 1984, for the purpose of converting alkanolamine such as MEA in situ to alkylene amine such as EDA by reaction with ammonia, and the EDA is in situ reacted with MEA according to the process of U.S. Pat. No. 4,036,881 to form alkyleneamines.

A summary of the prior art employing acid catalysts for making alkyleneamines is set forth in Table 1 below.

TABLE 1__________________________________________________________________________CITATION CATALYST TYPE REACTANTS__________________________________________________________________________U.S. Pat. No. 2,467,205 Silica gel, titania gel, alumina, Vapor phase condensation of thoria, aluminum phosphate. EDA over a fixed bed of the Preferred catalyst is basic catalyst, multipass process aluminum phosphate. shifts from polyethylene- polyamines with the first few cycles.U.S. Pat. No. 4,036,881 Phosphorus containing substances Alkanolamine and alkylene- selected from the group consisting amine in liquid phase reaction. of acidic metal phosphates, phosphoric acid compounds and their anhydrides, phosphorus acid compounds and their anhydrides, alkyl or aryl phosphate esters, alkyl or aryl phosphite esters, alkyl or aryl substituted phosphorous and phosphoric acids wherein said alkyl groups have from 1 to about 8 carbon atoms and said aryl groups have from 6 to about 20 carbon atoms, alkali metal monosalts of phosphoric acid, the thioanalogs of the fore- going, and mixtures of the above.U.S. Pat. No. 4,044,053 Phosphorus containing substances Alkanepolyols and alkylene- selected from the group consisting amine in liquid phase reaction. of acidic metal phosphates, phosphoric acid compounds and their anhydrides, phosphorus acid compounds and their anhydrides, alkyl or aryl phosphate esters, alkyl or aryl phosphate esters, alkyl or aryl substituted phosphorous acids and phosphoric acids wherein said alkyl groups have from 1 to about 8 carbon atoms and said aryl groups have from 6 to about 20 carbon atoms, alkali metal mono- salts of phosphoric acid and mixtures of the above.U.S. Pat. No. 4,314,083 Salt of a nitrogen or sulfur con- Alkanolamine and an taining substance or the corres- alkyleneamine in liquid ponding acid. phase reaction.U.S. Pat. No. 4,316,840 Metal nitrates and sulfates Reforming linear polyamines. including zirconium sulfate.U.S. Pat. No. 4,316,841 Phosphate, preferably boron Reforming linear polyamines. phosphate.U.S. Pat. No. 4,324,917 Phosphorus-containing cation Alkanolamine and an alkylene- exchange resin. amine in linquid phase reaction.U.S. Pat. No. 4,362,886 Arsenic, antimony or bismuth Alkanolamine and an alkylene- containing compounds. Antimony amine in liquid phase reaction. sulfate specifically disclosed.U.S. Pat. No. 4,399,308 Lewis acid halide. Alkanolamine and an alkylene- amine in liquid phase reaction.U.S. Pat. No. 4,394,524 Phosphorus-containing substance Ammonia, alkanolamine and an or salt of a sulfur-containing alkyleneamine in liquid phase substance, or the corresponding reaction. acidU.S. Pat. No. 4,448,997 Reacts alumina with phosphoric EDA with MEA. acid, adds ammonium hydroxide.U.S. Pat. No. 4,463,193 Group IIIB metal acid phosphate. Ammonia, alkanolamine and an alkyleneamine.U.S. Pat. No. 4,503,253 Supported phosphoric acid. Ammonia, alkanolamine and an alkyleneamine.U.S. Pat. No. 4,521,600 Select hydrogen phosphates and Alkanolamine and an alkylene- pyrophosphates. amine.U.S. Pat. No. 4,524,143 Phosphorus impregnated onto Alkanolamine and an alkylene- zirconium silicate support. amine.U.S. Pat. No. 4,540,822 Phosphorus compound deposited Alkanolamine and an alkylene- on a Group IVB metal oxide amine, regenerates the support. catalyst with O.sub.2 -containing gas.U.S. Pat. No. 4,547,591 Silica-alumina alone or in An ethyleneamine and an combination with an acidic alkanolamine; ethyleneamines; phosphorus cocatalyst. or ammonia and an alkanolamineU.S. Pat. No. 4,550,209 An intercalatively catalytically EDA and MEA. active tetravalent zirconium polymeric reaction product of an organo phosphonic acid or an ester thereof with a compound of tetravalent zirconium reactive therewith.U.S. Pat. No. 4,552,961 Phosphorus amide compound. Alkyleneamine and alkanolamine and/or alkylene glycol.U.S. Pat. No. 4,555,582 Phosphorus chemically bonded to MEA and EDA. a zirconium silicate support.U.S. Pat. No. 4,560,798 Rare earth metal or strontium MEA. acid phosphate.U.S. Pat. No. 4,578,517 Group IIIB metal acid phosphate. Ammonia or p-/s-amine and alkanolamine.U.S. Pat. No. 4,578,518 Thermally activated, calcined, MEA and EDA. pelleted titania containing titanium triphosphate. ". . . the titania that was used was . . . anatase." (Col. 9, lines 18-19).U.S. Pat. No. 4,578,519 Thermally activated, calcined, MEA and EDA with optional pelleted titania with chemically recycle of DETA. bonded phosphorus derived from polyphosphoric acid.U.S. Pat. No. 4,584,405 Activated carbon, optionally MEA and EDA. treated to incorporate phosphorus. Activated carbon may be washed with strong mineral acid to remove impurities followed by water wash. Optional treatment follows.U.S. Pat. No. 4,584,406 Pelleted Group IVB metal oxide MEA and EDA. with chemically bonded phosphorus derived from phosphoryl chloride or bromide.U.S. Pat. No. 4,588,842 Thermally activated pelleted MEA and EDA. Group IVB metal oxide with chemically bonded phosphorus.U.S. Pat. No. 4,605,770 Group IIA or IIIB metal acid Alkanolamine and an phosphate. alkyleneamine "in liquid phase".U.S. Pat. No. 4,609,761 Thermally activated pelleted MEA and EDA. titania with chemically bonded phosphorus.U.S. Pat. No. 4,612,397 Thermally activated pelleted MEA and EDA. titania with chemically bonded phosphorus.U.S. Pat. No. 4,617,418 Acid catalysts, mentions "beryl- Ammonia, alkanolamine and lium sulfate". an alkyleneamine "under vapor phase conditions".Japanese Patent Variety of phosphorus and metal Ammonia, alkanolamine andApplication phosphates including Group IVB ethyleneamine, with ammonia/#1983-185,871, phosphates. alkanolamine molar ratioPublication greater than 11.#1985-78,945U.S. Pat. No. 4,683,335 Tungstophosphoric acid, molybdo- Claims reaction of MEA and phosphoric acid or mixtures. EDA, but discloses self- deposited on titania. Examples condensation reaction of 2-7 characterize titania surface EDA and DETA. areas of 51, 60 and 120 m.sup.2 /gm.Japanese Patent Group IVB metal oxide with Ammonia and MEA.Application bonded phosphorus.#1985-078,391,Publication#1986-236,752Japanese Patent Group IVB metal oxide with Ammonia and MEA.Application bonded phosphorus.#1985-078,392,Publication#1986-236,753U.S. Pat. No. 4,698,427 Titania having phospshorus Diethanolamine and/or thermally chemically bonded hydroxyethyldiethylene- to the surface thereof in the triamine in EDA. form of phosphate bonds.U.S. Pat. No. 4,806,517 Pelleted Group IVB metal oxide MEA and EDA. with phosphorus thermally chemically bonded to the surface thereof.__________________________________________________________________________

This invention is directed to a new process for condensing amino compounds which depends on the novel concept of using Group IVB (Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 67th Ed., 1986-1987, inside cover) metal oxide catalysts, preferably on high surface area Group IVB metal oxide catalysts. The invention also relates to new high surface area Group IVB metal oxide catalysts containing one or more performance moderators.

SUMMARY OF THE INVENTION

The invention relates to a process of making amines which comprises condensing an amino compound in the presence of a Group IVB metal oxide condensation catalyst.

This invention relates to a process of making amines by the (i) intramolecular condensation of an amino compound to an amine having a lower molecular weight or (ii) the intermolecular condensation of an amino compound with one or more of another amino compound or a compound containing an alcoholic hydroxyl group using solid Group IVB metal oxides as the condensation catalyst. In one preferred embodiment of the invention, the solid Group IVB metal oxides used as the condensation catalyst possess a high surface area. The preferred process involves the manufacture of alkyleneamines, most desirably polyalkylenepolyamines, by such condensation reactions utilizing titanium dioxide, titanium oxide, zirconium oxide, or mixtures of them, and the like, as the condensation catalyst.

The invention also relates to amines condensation catalysts comprising high surface area, solid Group IVB metal oxides, preferably in particulate form.

The invention is also directed to a catalyst composition comprising a high surface area Group IVB metal oxide condensation catalyst containing a performance modifier. The preferred catalyst is a solid, particulate high surface area Group IVB metal oxide condensation catalyst containing a performance modifier.

As used herein, the term "amino compound" embraces ammonia and any compound containing nitrogen to which is bonded an active hydrogen. Also, as used herein, the term "oxide" embraces oxides, hydroxides and/or mixtures thereof.

For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 67th Ed , 1986-87, inside cover. Also, for purposes of this invention, Group IIIB metal oxides embraces the lanthanides and actinides.

DETAILED DESCRIPTION

This invention contemplates the catalyzed condensation by (i) intramolecular condensation of an amino compound to an amine having a lower molecular weight and (ii) intermolecular condensation of an amino compound with one or more of another amino compound or a compound containing an alcohol hydroxyl group to an amine having a lower, same or higher molecular weight than the reactants in the presence of solid Group IVB metal oxide condensation catalyst, preferably a high surface area solid Group IVB metal oxide condensation catalyst.

The high surface area Group IVB metal oxide condensation catalyst suitable for use in the practice of this invention comprise any of their active forms. Such forms are characterized as a degree of metal oxide condensation which provides sufficient residual bound hydroxyl groups or other groupings which render the metal oxide active.

The Group IVB metal oxides are typically formed by the hydrolysis and condensation of a suitable Group IVB metal in a hydrolyzable form, such as

MX.sub.a +H.sub.2 O.fwdarw.MX.sub.n (OH).sub.4-n +HX MX.sub.n (OH).sub.4-n .fwdarw.MO.sub.2 X.sub.m wherein M is a Group IVB metal such as titanium, zirconium or the like; X is a hydrolyzable group such as hydroxyl, halogen, sulfonyl or sulfate, phosphonyl, phosphoryl or phosphate, nitroso or nitrate, alkoxy of 1 to 8 carbon atoms, and the like; a is 3 or 4; n is a number less than about 2; and m has a value which constitutes less than about 10 weight percent of MO.sub.2 X.sub.m.

The level of activity of the catalyst of the invention is that level which of itself makes the catalyst at least as active in the condensation of amines as, for example, is phosphoric acid on an equivalent basis. Preferably, the Group IVB metal oxide catalyst has a surface area greater than about 70 m.sup.2 /gm to as high as about 260 m.sup.2 /gm or greater depending upon which Group IVB metal oxide that is employed. In the case of titanium oxides, the surface area should be greater than about 140 m.sup.2 /gm to as high as about 260 m.sup.2 /gm, more preferably, greater than about 160 m.sup.2 /gm to as high as about 260 m.sup.2 /gm, determined according to the single point N.sub.2 method. In the case of zirconia oxides, the surface area should be greater than about 70 m.sup.2 /gm to as high as about 150 m.sup.2 /gm, more preferably, greater than about 90 m.sup.2 gm to as high as about 135 m.sup.2 /gm, determined according to the single point N.sub.2 method. It is appreciated that the metal oxides described below which can be used in association with the Group IVB metal oxide and the performance moderators described below can affect the surface area of the Group IVB metal oxide catalyst. While surface areas described above may be preferred, for purposes of this invention, the surface area of the Group IVB metal oxide catalyst should be sufficient to contribute to product selectivity, catalytic activity and/or mechanical or dimensional strength of the catalyst.

Embraced within the scope of the Group IVB metal oxide catalysts of this invention are mixed metal oxides wherein at least one of the metals is titanium, zirconium or the like. Preferred metal oxides are amphoteric or slightly acidic or slightly basic. Illustrative of such metal oxides which may be utilized in association with the Group IVB metal oxide catalyst include, for example, one or more of the following: Group IA metal oxides, Group IIA metal oxides, Group IIIB metal oxides (including lanthanides and actinides), Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VIII metal oxides, Group IB metal oxides, Group IIB metal oxides, Group IIIA metal oxides, Group IVA metal oxides, Group VA metal oxides, Group VIA metal oxides and other Group IVB metal oxides or mixtures thereof. For mixed metal oxides in which at least one of the metals is titanium, suitable metals in association with titanium may include, for example, one or more of the following: Group IIIB metals such as scandium, yttrium and lanthanum including the lanthanides, Group VB metals such as niobium and tantalum, Group VIB metals such as chromium, molybdenum and tungsten, Group VIII metals such as iron, cobalt and nickel, Group IIB metals such as zinc and cadmium, Group IIIA metals such as boron, aluminum, gallium and indium, Group IVA metals such as silicon, germanium, tin and lead, Group VA metals such as arsenic, antimony and bismuth, and Group IVB metals such as zirconium and hafnium. For mixed metal oxides in which at least one of the metals is zirconium, suitable metals in association with zirconium may include, for example, one or more of the following: Group IVA metals such as silicon, germanium, tin and lead, Group VB metals such as niobium and tantalum, and Group VIB metals such as chromium, molybdenum and tungsten. The virtue of these metal oxides is that they demonstrate higher mechanical strength than the Group IVB metal oxide component per se and can contribute to product selectivity and catalytic activity.

Illustrative of mixed metal oxide catalysts embraced within the scope of this invention include, for example, TiO.sub.2 --SiO.sub.2, TiO.sub.2 --Al.sub.2 O.sub.3, TiO.sub.2 --CdO, TiO.sub.2 --Bi.sub.2 O.sub.3, TiO.sub.2 --Sb.sub.2 O.sub.5, TiO.sub.2 --SnO.sub.2, TiO.sub.2 --ZrO.sub.2, TiO.sub.2 --BeO, TiO.sub.2 MgO, TiO.sub.2 --CaO, TiO.sub.2 --SrO, TiO.sub.2 --ZnO, TiO.sub.2 --Ga.sub.2 O.sub.3, TiO.sub.2 --Y.sub.2 O.sub.3, TiO.sub.2 --La.sub.2 O.sub.3, TiO.sub.2 --MoO.sub.3, TiO.sub.2 --Mn.sub.2 O.sub.3, TiO.sub.2 --Fe.sub.2 O.sub.3, TiO.sub.2 --Co.sub.3 O.sub.4, TiO.sub.2 --WO.sub.3, TiO.sub.2 --V.sub.2 O.sub.5, TiO.sub.2 --Cr.sub.2 O.sub.3, TiO.sub.2 --ThO.sub.2, TiO.sub.2 --Na.sub.2 O, TiO.sub.2 --BaO, TiO.sub.2 --CaO, TiO.sub.2 --HfO.sub.2, TiO.sub.2 --Li.sub.2 O, TiO.sub.2 --Nb.sub.2 O.sub.5, TiO.sub.2 --Ta.sub.2 O.sub.5, TiO.sub.2 --Gd.sub.2 O.sub.3, TiO.sub.2 --Lu.sub.2 O.sub.3, TiO.sub.2 --Yb.sub.2 O.sub.3, TiO.sub.2 --CeO.sub.2, TiO.sub.2 --Sc.sub.2 O.sub.3, TiO.sub.2 --PbO, TiO.sub.2 --NiO, TiO.sub.2 --CuO, TiO.sub.2 --CoO, TiO.sub.2 --B.sub.2 O.sub.3, ZrO.sub.2 --SiO.sub.2, ZrO.sub.2 --Al.sub.2 O.sub.3 , ZrO.sub.2 --SnO, ZrO.sub.2 --PbO, ZrO.sub.2 --Nb.sub.2 O.sub.5, ZrO.sub.2 --Ta.sub.2 O.sub.5, ZrO.sub.2 --Cr.sub.2 O.sub.3, ZrO.sub.2 --MoO.sub.3, ZrO.sub.2 --WO.sub.3, ZrO.sub.2 --TiO.sub.2, ZrO.sub.2 --HfO.sub.2, TiO.sub.2 --SiO.sub.2 --Al.sub.2 O.sub.3, TiO.sub.2 --SiO.sub.2 --ZnO, TiO.sub.2 --SiO.sub.2 --ZrO.sub.2, TiO.sub.2 --SiO.sub.2 --CuO, TiO.sub.2 --SiO.sub.2 --MgO, TiO.sub.2 --SiO.sub.2 --Fe.sub.2 O.sub.3, TiO.sub.2 --SiO.sub.2 --B.sub.2 O.sub.3, TiO.sub.2 --SiO.sub.2 --WO.sub.3, TiO.sub.2 --SiO.sub.2 --Na.sub.2 O, TiO.sub.2 --SiO.sub.2 --MgO, TiO.sub.2 --SiO.sub.2 --La.sub.2 O.sub.3, TiO.sub.2 --SiO.sub.2 --Nb.sub.2 O.sub.5, TiO.sub.2 --SiO.sub.2 --Mn.sub.2 O.sub.3, TiO.sub.2 --SiO.sub.2 --Co.sub.3 O.sub.4, TiO.sub.2 --SiO.sub.2 --NiO, TiO.sub.2 --SiO.sub. 2 --PbO, TiO.sub.2 --SiO.sub.2 --Bi.sub.2 O.sub.3, TiO.sub.2 --Al.sub.2 O.sub.3 --ZnO, TiO.sub.2 --Al.sub.2 O.sub.3 --ZrO.sub.2, TiO.sub.2 --Al.sub.2 O.sub.3 --Fe.sub.2 O.sub.3, TiO.sub.2 --Al.sub.2 O.sub.3 --WO.sub.3, TiO.sub.2 --Al.sub.2 O.sub.3 --La.sub.2 O.sub.3, TiO.sub.2 --Al.sub.2 O.sub.3 --Co.sub.3 O.sub.4, ZrO.sub.2 --SiO.sub.2 --Al.sub.2 O.sub.3, ZrO.sub.2 --SiO.sub.2 --SnO, ZrO.sub.2 --SiO.sub.2 --Nb.sub.2 O.sub.5, ZrO.sub.2 --SiO.sub.2 --WO.sub.3, ZrO.sub.2 --SiO.sub.2 --TiO.sub.2, ZrO.sub.2 --SiO.sub.2 --MoO.sub.3, ZrO.sub.2 --SiO.sub.2 --HfO.sub.2, ZrO.sub.2 --SiO.sub.2 --Ta.sub.2 O.sub.5, ZrO.sub.2 --Al.sub.2 O.sub.3 --SiO.sub.2, ZrO.sub.2 --Al.sub.2 O.sub.3 --PbO, ZrO.sub.2 --Al.sub.2 O.sub.3 --Nb.sub.2 O.sub.5, ZrO.sub.2 --Al.sub.2 O.sub.3 --WO.sub.3, ZrO.sub.2 --Al.sub.2 O.sub.3 --TiO.sub.2, ZrO.sub.2 --Al.sub.2 O.sub.3 --MoO.sub.3, ZrO.sub.2 --HfO.sub.2 --Al.sub.2 O.sub.3, ZrO.sub.2 --HfO.sub.2 --TiO.sub.2, and the like. Other suitable mixed metal oxide catalysts embraced within the scope of this invention are disclosed by Tanabe et al., Bulletin of the Chemical Society of Japan, Vol. 47(5), pp. 1,064-1,066 (1974).

The metal oxides described herein which can be used in association with the Group IVB metal oxide may contribute to product selectivity and/or catalytic activity of the reaction and/or stability of the catalyst. The catalyst structure can comprise from about 0 to about 50 percent by weight of the metal oxide, preferably from about 0 to about 25 percent by weight of the metal oxide, and more preferably from about 0 to about 10 percent by weight of the metal oxide, the remainder being the weight of the Group IVB metal oxide. For mixed metal oxides containing titania, higher concentrations of titania can provide very desirable product selectivities including acyclic to cyclic selectivities and linear to branched selectivities of higher polyalkylene polyamine products. As discussed hereinafter, the Group IVB metal oxide catalyst of this invention may also contain support(s), binding agent(s) or other additives to stabilize or otherwise help in the manufacture of the catalyst.

Though the Group IVB metal oxide catalyst of the invention provides sufficient activity to effect the condensation reaction, certain combinations of reactants and/or product formation are benefited by treating the catalyst with a catalyst moderator, hereinafter termed "performance moderator." Catalyst moderators are widely used to control the performance of catalysts in areas of selectivity to certain products and the repression of a catalyst's proclivity to generate a broad range of reaction products. It has been found that there are a range of materials that impact the Group IVB metal oxide catalysts of this invention in the variety of reaction products. The performance moderator may be any material which impacts the Group IVB metal oxide catalyst's selection of reaction products or which changes the proportion of any one or more of the reaction products which the Group IVB metal oxide catalyst generates at comparable processing conditions In addition to contributing to product selectivity, the performance moderator may be any material which contributes to catalytic activity and/or catalyst stability (mechanical or dimensional strength).

A preferred performance moderator is a mineral acid or a compound derived from a mineral acid. Suitable for use as performance moderators are one or more phosphoric acid or a salt of phosphoric acid, hydrogen fluoride, hydrofluoric acid or a fluoride salt, sulfuric acid or a salt of sulfuric acid, and the like. The moderator may also be organic esters of phosphoric acid or a salt of phosphoric acid, hydrogen fluoride organic complexes, hydrofluoric acid organic complexes or a fluoride salt organic complexes, organic esters of sulfuric acid or a salt of sulfuric acid, and the like. Suitable salts of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate and the like. Other preferred performance moderators include the metal oxides described above which can be used in association with the Group IVB metal oxide and also metallic phosphates which may or may not have a cyclic structure and metallic polyphosphates which may or may not have a condensed structure described below such as sodium trimetaphosphate, sodium tripolyphosphate, disodium dihydrogen pyrophosphate and the like including mixtures thereof.

It has been noted that the selectivity to a particular reaction product can be materially influenced by a particular performance moderator. For example, the addition of ammonium fluoride or diammonium sulfate to the Group IVB metal oxide catalyst of the invention produces diethylenetriamine (DETA) almost exclusively from the reaction of ammonia and ethylenediamine (EDA) with aminoethylethanolamine (AEEA). No other performance moderator has been found to have such an effect on the Group IVB metal oxide catalyst of this invention.

The metal oxides described hereinabove which can be used in association with the Group IVB metal oxide can also be used as performance moderators in accordance with this invention. The metal oxides can contribute to product selectivity, catalytic activity and/or catalyst stability (mechanical strength).

The metallic phosphates and polyphosphates are preferred performance moderators for use in this invention. The metallic phosphate and polyphosphate condensation catalysts may or may not have a cyclic structure and may or may not have a condensed structure. Suitable metallic phosphates having a cyclic structure or an acyclic structure are disclosed in U.S. patent application Ser. No. 390,706, filed on an even date herewith and incorporated herein by reference. Suitable metallic polyphosphates having a condensed structure are disclosed in U.S. patent application Ser. No. 390,709, filed on an even date herewith and incorporated herein by reference. Illustrative of metallic phosphates which may or may not have a cyclic structure and metallic polyphosphates which may or may not have a condensed structure include, for example, metallic orthophosphates (PO.sub.4 .sup.-3), metallic pyrophosphates P.sub.2 O.sub.7 .sup.-4), metallic polyphosphates (including tripolyphosphates (P.sub.3 O.sub.10 .sup.-5), tetrapolyphosphates (P.sub.4 O.sub.13 .sup.-6), pentapolyphosphates (P.sub.5 O.sub.16 .sup.-7) and higher polyphosphates), metallic metaphosphates (including trimetaphosphates (P.sup.3 O.sub.9 .sup.-3), tetrametaphosphates (P.sub.4 O.sub.12 .sup.-4) and other lower and higher metaphosphates) and metallic ultraphosphates (condensed phosphates containing more P.sub.2 O.sub.5 than corresponds to the metaphosphate structure). Corresponding metallic metaphosphimates, metallic phosphoramidates and metallic amido- and imidophosphates of the above may also be used as performance moderators in accordance with this invention. Suitable metals which can be incorporated into the performance moderators include, for example, Group IA metals, Group IIA metals, Group IIIB metals, Group IVB metals, Group VB metals, Group VIB metals, Group VIIB metals, Group VIII metals, Group IB metals, Group IIB metals, Group IIIA metals, Group IVA metals, Group VA metals, Group VIA metals and mixtures thereof. Such metallic phosphates and metallic polyphosphates can contribute to product selectivity, catalytic activity and/or catalyst stability (mechanical strength).

Illustrative of metallic orthophosphates which may be utilized in this invention include, for example, NaH.sub.2 PO.sub.4, KH.sub.2 PO.sub.4, RbH.sub.2 PO.sub.4, LiH.sub.2 PO.sub.4, MgHPO.sub.4, CaHPO.sub.4, YPO.sub.4, CePO.sub.4, LaPO.sub.4, ThPO.sub.4, MnPO.sub.4, FePO.sub.4, BPO.sub.4, AlPO.sub.4, BiPO.sub.4, Mg(H.sub.2 PO.sub.4).sub.2, Ba(H.sub.2 PO.sub.4).sub.2, Mg(NH.sub.4).sub.2 PO.sub.4, Ca(H.sub.2 PO.sub.4).sub.2, La(H.sub.2 PO.sub.4).sub.3 and the like. Illustrative of metallic pyrophosphates which may be utilized in this invention include, for example, dNa.sub.2 H.sub.2 P.sub.2 O.sub.7, K.sub.2 H.sub.2 P.sub.2 O.sub.7, Ca.sub.2 P.sub.2 O.sub.7, Mg.sub.2 P.sub.2 O.sub.7, KMnP.sub.2 O.sub.7, AgMnP.sub.2 O.sub.7, BaMnP.sub.2 O.sub.7, NaMnP.sub.2 O.sub.7, KCrP.sub.2 O.sub.7, NaCrP.sub.2 O.sub.7, Na.sub.4 P.sub.2 O.sub.7,K.sub.4 P.sub.2 O.sub.7, Na.sub.3 HP.sub.2 O.sub.7, NaH.sub.3 P.sub.2 O.sub.7, SiP.sub.2 O.sub.7, ZrP.sub.2 O.sub.7, Na.sub.6 Fe.sub.2 (P.sub.2 O.sub.7).sub.3, Na.sub.8 Fe.sub.4 (P.sub.2 O.sub.7).sub.5, Na.sub.6 Cu(P.sub.2 O.sub.7).sub.2, Na.sub.32 Cu.sub.14 (P.sub.2 O.sub.7).sub.15, Na.sub.4 Cu.sub.18 (P.sub.2 O.sub.7).sub.5, Na.sub.2 (NH.sub.4).sub.2 P.sub.2 O.sub.7, Ca(NH.sub.4).sub.2 P.sub.2 O.sub.7, MgH.sub.2 P.sub.2 O.sub.7, Mg(NH.sub.4).sub.2 P.sub. 2 O.sub.7 and the like. Illustrative of metallic polyphosphates which may be utilized in this invention include, for example, NaSr.sub.2 P.sub.3 P.sub.10, NaCa.sub.2 P.sub.3 O.sub.10, NaNi.sub.2 P.sub.3 O.sub.10, Na.sub.5 P.sub.3 O.sub.10, K.sub.5 P.sub.3 O.sub.10, Na.sub.3 MgP.sub.3 O.sub.10, Na.sub.3 CuP.sub.3 O.sub.10, Cu.sub.5 (P.sub.3 O.sub.10).sub.2, Na.sub.3 ZnP.sub.3 O.sub.10, Na.sub.3 CdP.sub.3 O.sub.10, Na.sub.6 Pb(P.sub.3 O.sub.10).sub.2, Na.sub.3 CoP.sub.3 O.sub.10, K.sub.3 CoP.sub.3 O.sub.10, Na.sub.3 NiP.sub.3 O.sub.10, K.sub.2 (NH.sub.4).sub.3 P.sub.3 O.sub.10, Ca(NH.sub.4).sub.2 P.sub.3 O.sub.10, La(NH.sub.4).sub.2 P.sub.3 O.sub.10, NaMgH.sub.2 P.sub.3 O.sub.10 and the like. Illustrative of metallic metaphosphates which may be utilized in this invention include, for example, Na.sub.3 P.sub.3 O.sub.9, K.sub.3 P.sub.3 O.sub.9, Ag.sub.3 P.sub.3 O.sub.9, Na.sub.4 P.sub. 4 O.sub.12, K.sub.4 P.sub.4 O.sub.12, Na.sub.2 HP.sub.3 O.sub.9, Na.sub.4 Mg(P.sub.3 O.sub.9).sub.2, NaSrP.sub.3 O.sub.9, NaCaP.sub.3 O.sub.9, NaBaP.sub.3 O.sub.9, KBaP.sub.3 O.sub.9, Ca.sub.3 (P.sub.3 O.sub.9).sub.2, Ba(P.sub.3 O.sub.9).sub.2, Na.sub.2 Ni.sub.2 (P.sub.3 O.sub.9).sub.2, Na.sub.4 Co(P.sub.3 O.sub.9).sub.2, Na.sub.4 Cd(P.sub.3 O.sub.9).sub.2 and the like. Illustrative of metallic ultraphosphates which may be utilized in this invention include, for example, CaP.sub.4 O.sub.11, Ca.sub.2 P.sub.6 O.sub.17, Na.sub.8 P.sub.10 O.sub.29, Na.sub.6 P.sub.8 O.sub.23, Na.sub.2 CaP.sub.6 O.sub.17, Na.sub.2 P.sub.4 O.sub.11, NaBaP.sub.7 O.sub.18, Na.sub.2 P.sub.8 O.sub.21, K.sub.4 P.sub.6 O.sub.17 and the like. Preferred performance moderators for use in this invention include Group IA metal dihydrogen orthophosphates, Group IA metal metaphosphates and Group IA metal dihydrogen pyrophosphates, more preferably NaH.sub.2 PO.sub. 4, Na.sub.3 P.sub.3 O.sub.9 and Na.sub.2 H.sub.2 P.sub.2 O.sub.7. Other suitable metallic phosphates and metallic polyphosphates which are embraced within the scope of this invention are disclosed by Van Wazer, J. R., Phosphorus and Its Compounds, Vol. 1, Interscience Publishers, Inc., New York (1958).

Group VIB metal-containing substances may be used as performance moderators in accordance with this invention. Suitable Group VIB metal-containing substances are disclosed in U.S. patent application Ser. No. 390,708, filed on an even date herewith and incorporated herein by reference. Illustrative of Group VIB metal-containing performance moderators include, for example, one or more oxides of tungsten, chromium, molybdenum or mixtures thereof.

A variety of conventional phosphorus-containing substances may be suitable for use as performance moderators in this invention. The conventional substances should be capable of functioning as a performance moderator. Illustrative of conventional phosphorus-containing substances may include, for example, those disclosed in U.S. Pat. No. 4,036,881, U.S. Pat. No. 4,806,517, U.S. Pat. No. 4,617,418, U.S. Pat. No. 4,720,588, U S. Pat. No. 4,394,524, U.S. Pat. No 4,540,822, U.S. Pat. No. 4,588,842, U.S. Pat. No. 4,605,770, U.S. Pat. No. 4,683,335, U.S. Pat. No. 4,316,841, U.S. Pat. No. 4,463,193, U.S. Pat. No. 4,503,253, U.S. Pat. No. 4,560,798 and U.S. Pat. No. 4,578,517.

Suitable conventional phosphorus-containing substances which may be employed as performance moderators in this invention include acidic metal phosphates, phosphoric acid compounds and their anhydrides, phosphorous acid compounds and their anhydrides, alkyl or aryl phosphate esters, alkyl or aryl phosphite esters, alkyl or aryl substituted phosphorous acids and phosphoric acids, alkali metal monosalts of phosphoric acid, the thioanalogs of the foregoing, and mixtures of any of the above.

The amount of the performance moderator of the mineral acid type used with the Group IVB metal oxide catalyst of the invention is not narrowly critical. Generally, the amount does not exceed 25 weight percent of the weight of the catalyst. As a rule, it is desirable to use at least 0.01 weight percent of the weight of the catalyst. Preferably, the amount of performance moderator, when used, will range from about 0.2 to about 10 weight percent of the weight of the catalyst. Most preferably, the amount of performance moderator, when used, will range from about 0.5 to about 5 weight percent of the weight of the catalyst.

The amount of performance moderator other than the mineral acid type used with the Group IVB metal oxide catalyst is not narrowly critical. Generally, the amount does not exceed 50 weight percent of the weight of the catalyst. The amount of performance moderator can range from about 0 to about 50 weight percent of the weight of the catalyst, preferably from about 0 to about 25 weight percent of the weight of the catalyst, and more perferably from about 0 to about 15 weight percent of the weight of the catalyst. Most preferably, the amount of performance moderator, when used, will range from about 0.5 to about 10 weight percent of the weight of the catalyst.

This invention also embraces the use of vicinal di(hetero)alkylene organometalates in the preparation of amines. Suitable vicinal di(hetero)alkylene organometalates in U.S. patent application Ser. No. 390,828, filed on an even date herewith and incorporated herein by reference.

The performance moderator can be provided to the Group IVB metal oxide catalyst by conventional procedures known in the art. For example, the performance moderator can be provided to the catalyst by impregnating particles or monolithic structures comprising the Group IVB metal oxide catalyst with liquid comprising the performance moderator. This is a well known procedure in the art for incorporating additives to a solid support material. The Group IVB metal oxide catalyst of the invention may be utilized as solid powders, such as a pigment form of the Group IVB metal oxide, or as fused, bonded or compressed solid pellets, or larger structures comprising the Group IVB metal oxide, or as coated, fused, bonded or compressed solid pellets, or larger structures, composited with one or more support materials, comprising the Group IVB metal oxide. These solid structures may be treated with the performance moderator by mixing a liquid body of the performance moderator with the solid structure. For example, the Group IVB metal oxide solids may be slurried in the performance moderator, drained, washed and suctioned to remove excess performance moderator, and then dried with heat to remove any volatiles accompanying the performance moderator. The drying temperature chosen will depend on the nature of the volatiles to be removed. Usually, the time/temperature for effecting drying will be below the conditions for effecting dehydration to remove bound water from the Group IVB metal oxide. Normally the drying temperature will be greater than about 120.degree. C. and below about 600.degree. C. The drying time will generally go down as the drying temperature rises and vice versus, and may extend from 5 seconds to about 24 hours.

Alternatively, the performance moderator can be provided to the catalyst at the time of preparing the Group IVB metal oxide. For example, the Group IVB metal oxide and one or more other metal oxides may be condensed from their respective hydrolyzable monomers described below to the desired oxides to form oxide powders which can thereafter be blended and compressed to form pellets and larger structures of the Group IVB metal oxide catalyst of this invention. The one or more metal oxides which can be used in association with the Group IVB metal oxide in accordance with this invention can be provided from metal salts which can be heated to form the metal oxide as illustrated in the Examples hereinafter. It is appreciated that the performance moderator can be incorporated into the molecular bonding configuration of the Group IVB metal oxide by conventional procedures known in the art.

The Group IVB metal oxide catalysts of the invention prior to the optional treatment of the performance moderator may be prepared in a wide variety of ways. The Group IVB metal oxide may be provided as a partial condensate to the MO.sub.2 X.sub.q state, where q has a higher value than m, supra, on a support, such as a silica or alpha, beta or gamma alumina, silicon carbide, and the like, and then condensed to the desired degree of acidity by heating to effect polymerization to the desired oxide form. The Group IVB metal oxide may be condensed from the hydrolyzable monomers characterized above to the desired oxide, indeed, to form an oxide powder which can thereafter be compressed in the presence of binding agents to form pellets and larger structures of the Group IVB metal oxide catalyst of the invention. A blend of the powder and binding agent can be made into a shapeable paste which can be extruded and cut into pellets according to conventional procedures. The extrudate may thereafter be fired to cure the binding agent and fix the structure. The cut extrudate may be blended with a support material such as those characterized above, and the blend fired to fuse the Group IVB metal oxide catalyst to the support.

A preferred catalyst structure comprises the Group IVB metal oxide having a surface area of at least 140 m.sup.2 /gm bonded to a support material. The term "support," as used herein and in the claims, means a solid structure which does not adversely affect the catalytic properties of the Group IVB metal oxide and is at least as stable as the Group IVB metal oxide catalyst to the reaction medium. The support can function as an amine condensation catalyst independent of the Group IVB metal oxide, although it may have lower catalytic activity to the reaction The support may act in concert with the catalyst to moderate the reaction. It has been noted that some supports, such as gamma-alumina, appear to contribute to the selectivity of the reaction. The catalyst structure can comprise from about 2 to about 50 percent by weight or greater of the support, preferably from about 2 to about 25 percent by weight of the support, and more preferably from about 2 to about 10 percent by weight of the support, the remainder being the weight of the Group IVB metal oxide catalyst. Included in the weight of the support is the weight of any binding agent such as phosphates, sulfates, silicates, fluorides, and the like, and any other additive provided to stabilize or otherwise help in the manufacture of the catalyst. The support may be particles as large or larger than the catalyst component and "glued" to the catalytic Group IVB metal oxide by virtue of a binding medium.

The support may constitute a separate phase in the process of extruding the catalytic structure. In this embodiment, the support forming material, preferably as a paste is blended with a paste of the Group IVB metal oxide or a partial condensate thereof. The paste may comprise the oxide forms of the support and the oxide catalyst, each blended with water, and/or binding agents. The extrudate of the blend is passed through a multiorificed die and chopped into pellets of the desired size. The particles may be doughnut shaped, spherical, and the like. Then the particles are calcined to dry them and complete any condensation reaction in the support and/or the Group IVB metal oxide catalyst.

The use of supports for the Group IVB metal oxide catalyst provides a number of significant advantages. It has been determined that some of the Group IVB metal oxides are not as stable in the amines reaction media when utilized over an extended period of time. When the reaction is effected as a batch reaction, this matter is not a problem. However, when the reaction is effected with the Group IVB metal oxide catalyst as part of a fixed bed in a tubular reactor, the preferred procedure for carrying out the invention, it is desirable to have the catalyst be more stable. When the catalyst is combined with the support, the catalyst has greater stability for the reaction medium, and therefore, it is better able to be used in a fixed bed of a continuous reactor. The supported catalysts suffer from none of the leaching problems that the catalyst per se may have or the problems that are associated with the prior art catalysts, such as acidic phosphorus compounds on silica.

The reactants used in the condensation process of the invention may be ammonia or organic compound containing --NH-- and any compound possessing an alcoholic hydroxyl group, subject to the following: the intramolecular condensation of an amino compound produces an amine having a lower molecular weight, and the intermolecular condensation of an amino compound with one or more of another amino compound or a compound containing an alcoholic hydroxyl group produces an amine having a lower, same or higher molecular weight than the reactants.

Illustrative of suitable reactants in effecting the process of the invention, include by way of example:

Ammonia

MEA--monoethanolamine EDA--ethylenediamine MeEDA--methylethylenediamine EtEDA--ethylethylenediamine AEEA--N-(2-aminoethyl)ethanolamine HEP--N-(2-hydroxyethyl)piperazine DETA--diethylenetriamine AEP--N-(2-aminoethyl)piperazine TAEA--trisaminoethylamine TETA--triethylenetetramine TEPA--tetraethylenepentamine PEHA--pentaethylenehexamine

TETA Isomers

TAEA--trisaminoethylamine TETA--triethylenetetramine DPE--dipiperazinoethane DAEP--diaminoethylpiperazine PEEDA--piperazinoethylethylenediamine

TEPA Isomers

AETAEA--trisaminoethylamine TEPA--tetraethylenepentamine AEDPE--aminoethyldipiperazinoethane AEPEEDA--aminoethylpiperazinoethylethylenediamine iAEPEEDA--isoaminoethylpiperazinoethylethylenediamine AEDAEP--aminoethyldiaminoethylpiperazine BPEA bispiperazinoethylamine

The foregoing also can represent the products of the reaction. For example, ammonia and MEA are frequently employed to produce EDA along with a variety of other amines, most of which are set forth above. The higher polyalkylene polyamines prepared by the process of this invention such as TETA, TEPA and PEHA are very useful commercial products for a variety of applications including fuel oil additives, corrosion inhibitors, fabric softeners, fungicides and others.

Glycol compounds can also be employed in the preparation of amines in accordance with this invention. For purposes of this invention, glycol compounds embrace diols and polyols. Illustrative of suitable glycol compounds include alkylene glycols such as ethylene glycol, propylene glycol, 1,3-propane diol or mixtures thereof.

The process may be effected in the liquid or vapor or supercritical liquid states or mixtures thereof though the actual reaction is believed to occur on the catalyst's solid surface in the absorbed state. In this context, the vapor phase reaction is intended to refer to the general vapor state of the reactants. Though the reaction conditions may range from subatmospheric to superatmospheric conditions, it is desirable to run the reaction from about 50 psig to about 3,000 psig, preferably from about 200 psig to about 2,000 psig.

The temperature of the reaction may be as low as about 125.degree. C. to about 400.degree. C. Preferably, the reaction temperature ranges from about 150.degree. C. to about 350.degree. C., and most preferably from about 225.degree. C. to about 325.degree. C.

The reaction may be effected by the incremental addition of one of the reactants to the other or by the joint addition of the reactants to the catalyst. The preferred process effects the reaction in a continuous manner over a fixed bed of the Group IVB metal oxide catalyst in a tubular reactor. However, the reaction may be carried out by slurrying the catalyst in the reactants or in a batch mode in an autoclave. An inert such as nitrogen, methane and the like can be used in the reaction process.

The preferred process involves the formation of alkyleneamines from the intermolecular condensation of alkanolamines and alkyleneamines or the intramolecular condensation of alkyleneamines or alkanolamines. Illustrative of such reactions are the following reactant combinations:

______________________________________REACTANT REACTANT PRODUCTS______________________________________Ammonia Methanol Monomethylamine Dimethylamine TrimethylamineAmmonia MEA EDA, DETA, AEEA, TETA, TEPA, PIPAmmonia AEEA DETA, PIPMEA, Ammonia EDA EDA, AEEA, HEP, DETA, AEP, TETA, TEPA, PEHA, TETA Isomers: TAEA, TETA, DAEP, PEEDA, DPE TEPA, TEPA Isomers: AETAEA, AEPEEDA, AEDAEP, AEDPE, BPEAMEA EDA AEEA, HEP, DETA, AEP, TETA, TEPA, PEHA, TETA Isomers: TAEA, TETA, DAEP, PEEDA, DPE TEPA, TEPA Isomers: AETAEA, AEPEEDA, AEDAEP, AEDPE, BPEAEDA AEEA HEP, AEP, TETA, TEPA, PEHA, TETA Isomers: TAEA, TETA, DAEP, PEEDA, DPE TEPA, TEPA Isomers: AETAEA, AEPEEDA, AEDAEP, AEDPE, BPEADETA AEEA TEPA Isomers, AEPEDA EDA DETA, TETA and TEPA Isomers______________________________________

It is appreciated that the Group IVB metal oxide condensation catalysts of this invention may also be useful in the production of alkylamines. For example, an alcohol and at least one of ammonia, a primary amine, a secondary amine or a tertiary amine may be contacted in the presence of a Group IVB metal oxide condensation catalyst under conditions effective to produce alkylamines.

This invention is further illustrated by certain of the following examples:

EXAMPLES

In the examples set forth in Tables I-XXIV and XLV-LXXI below, the catalyst of choice was placed in a tubular reactor having an outside diameter of 1 inch and an overall length of 30 inches. The catalyst portion of the reactor comprised a length of 24 inches, accommodating 150 cubic centimeters of catalyst. The reactor was made of 316 stainless steel. In the examples set forth in Tables XXV-XLIV and LXXII-LXXIX, the catalyst of choice was placed in one of three tubular reactors, each having an outside diameter of 1 inch, and heated by a sand bath. The catalyst portion of the reactor comprised a length of 24 inches, accommodating 100 cubic centimeters of catalyst. As used herein, AB1 refers to a material obtained from Norton Company, Akron, Ohio, which is a mixture of sodium trimetaphosphate and sodium tripolyphosphate. As used in the tables below, acyclic (N4)/cyclic (.ltoreq.N4) refers to the weight ratio of TETA+TAEA to PIP+AEP+PEEDA+DAEP+DPE, and acyclic (N5)/cyclic (.ltoreq.N5) refers to the weight ratio of TEPA+AETAEA to PIP+AEP+PEEDA+DAEP+DPE+AEPEEDA+iAEPEEDA+AEDAEP+AEDPE+BPEA. The catalysts employed are identified as follows:

__________________________________________________________________________DESIGNATION COMPOSITION PHYSICIAL PROPERTIES__________________________________________________________________________A Titanium dioxide (anatase), 2% Particle size: 1/16" cylindrical sulfur (presumed to be --OSO.sub.3 H) extrudates: Surface area: 188.4 content m.sup.2 /gm; Pore vol. Hg, cc/gm: 0.274; Med. Pore Diam., 0.0092; Crush strength, FPCS, LBS.: 10.8.B TiO.sub.2 (anatase)-.gamma.-Al.sub.2 O.sub.3 Particle size: 1/16" cylindrical extrudates TiO.sub.2 -.gamma.-Al.sub.2 O.sub.3 ; Catalyst surface area: 162.8 m.sub.2 /gm.; Pore vol. N.sub.2, cc/gm.: 0.338.C TiO.sub.2 (anatase)-SiO.sub.2 Particle size: 1/16: cylindrical extrudates; TiO.sub.2 --SiO.sub.2 ; Catalyst surface area: 210.9 m.sup.2 /gm.; Pore vol. N.sub.2, cc/gm.: 0.334.D Catalyst B/small amount of Particle size: 1/16" cylindrical H.sub.3 PO.sub.4 from diammonium extrudates TiO.sub.2 -.gamma.-Al.sub.2 O.sub.3 ; hydrogen phosphate Catalyst surface area: 162.8 m.sub.2 /gm.; Pore vol. N.sub.2, cc/gm.: 0.338.E Catalyst C/small amount of Particle size: 1/16" cylindrical H.sub.3 PO.sub.4 from diammonium extrudates TiO.sub.2 --SiO.sub.2 ; Catalyst hydrogen phosphate surface area: 210.9 m.sup.2 /gm.; Pore vol. N.sub.2, cc/gm.: 0.334.F Catalyst B/small amount of HF Particle size: 1/16" cylindrical from NH.sub.4 F extrudates TiO.sub.2 -.gamma.-Al.sub.2 O.sub.3 ; Catalyst surface area: 162.8 m.sub.2 /gm.; Pore vol. N.sub.2, cc/gm.: 0.338.G Catalyst B/small amount of H.sub.2 SO.sub.4 Particle size: 1/16" cylindrical from (NH.sub.4).sub.2 SO.sub.4 extrudates TiO.sub.2 -.gamma.-Al.sub.2 O.sub.3 ; Catalyst surface area: 162.8 m.sub.2 /gm.; Pore vol. N.sub.2, cc/gm.: 0.338.H Catalyst C/small amount of HF from Particle size: 1/16: cylindrical NH.sub.4 F extrudates; TiO.sub.2 --SiO.sub.2 ; Catalyst surface area: 210.9 m.sup.2 /gm.; Pore vol. N.sub.2, cc/gm.: 0.334.I Catalyst C/small amount of Particle size: 1/16: cylindrical H.sub.2 SO.sub.4 from (NH.sub.4).sub.2 SO.sub.4 extrudates; TiO.sub.2 --SiO.sub.2 ; Catalyst surface area: 210.9 m.sup.2 /gm.; Pore vol. N.sub.2, cc/gm.: 0.334.J TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch SnO cylindrical extrudates; Catalyst surface area: 125.0 m.sup.2 /gm.K TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch H.sub.3 BO.sub.3 cylindrical extrudates; Catalyst surface area: 154.0 m.sup.2 /gm.L TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch Nb.sub.2 O.sub.5 /H.sub.3 VO.sub.4 cylindrical extrudates; Catalyst surface area: 111.0 m.sup.2 /gm.M TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch La.sub.2 O.sub.3 /H.sub.3 PO.sub.4 cylindrical extrudates; Catalyst surface area: 136.0 m.sup.2 /gm.N TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch La.sub.2 O.sub.3 cylindrical extrudates; Catalyst surface area: 136.0 m.sup.2 /gm.O TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch Nb.sub.2 O.sub.5 /H.sub.3 BO.sub.3 cylindrical extrudates; Catalyst surface area: 111.0 m.sup.2 /gm.P TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch H.sub.3 VO.sub.4 cylindrical extrudates; Catalyst surface area: 149 m.sup.2 /gm.Q TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch SnO/H.sub.3 PO.sub.4 cylindrical extrudates; Catalyst surface area: 125 m.sup.2 /gm.R TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 Particle size: 1/16 inch cylindrical extrudates; Catalyst surface area: 185 m.sup.2 /gm.S TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch SnO/H.sub.3 BO.sub.3 cylindrical extrudates; Catalyst surface area: 141 m.sup.2 /gm.T TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch La.sub.2 O.sub.3 /H.sub.3 VO.sub.4 cylindrical extrudates; Catalyst surface area: 148 m.sup.2 /gm.U TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Nb.sub.2 O.sub.5 /H.sub.3 PO.sub.4 cylindrical extrudates; Catalyst surface area: 129 m.sup.2 /gm.V TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Nb.sub.2 O.sub.5 cylindrical extrudates; Catalyst surface area: 146 m.sup.2 /gm.W TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch La.sub.2 O.sub.3 /H.sub.3 BO.sub.3 cylindrical extrudates; Catalyst surface area: 135 m.sup.2 /gm.X TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch SnO/H.sub.3 VO.sub.4 cylindrical extrudates; Catalyst surface area: 143 m.sup.2 /gm.Y TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch H.sub.3 PO.sub.4 cylindrical extrudates; Catalyst surface area: 150 m.sup.2 /gm.Z TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch La.sub.2 O.sub.3 /H.sub.3 PO.sub.4 cylindrical extrudates; Catalyst surface area: 139 m.sup.2 gm.AA TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Na.sub.2 B.sub.4 O.sub.7 cylindrical extrudates; Catalyst surface area: 99 m.sup.2 /gm.BB TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Na.sub.2 SnO.sub.6 cylindrical extrudates; Catalyst surface area: 112 m.sup.2 /gm.CC ZrO.sub.2 /SiO.sub.2 Particle size: 1/16 inch cylindrical extrudates; Catalyst surface area: 127 m.sup.2 /gm.DD ZrO.sub.2 /SiO.sub.2 / Particle size: 1/16 inch Nb.sub.2 O.sub.5 cylindrical extrudates; Catalyst surface area: 126 m.sup.2 /gm.EE ZrO.sub.2 /SiO.sub.2 / Particle size: 1/16 inch H.sub.3 BO.sub.3 cylindrical extrudates; Catalyst surface area: 126 m.sup.2 /gm.FF ZrO.sub.2 /SiO.sub.2 / Particle size: 1/16 inch NH.sub.4 VO.sub.3 (2 wt. % cylindrical extrudates; Catalyst as V.sub.2 O.sub.5) surface area: 169 m.sup.2 /gm.GG TiO.sub.2 (anatase)/SiO.sub.2 Particle size: 1/16 inch cylindrical extrudates; Catalyst surface area: 169 m.sup.2 /gm.HH TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Al.sub.2 O.sub.3 cylindrical extrudates; Catalyst surface area: 204 m.sup.2 /gm.II TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch B.sub.2 O.sub.3 cylindrical extrudates; Catalyst surface area: 219 m.sup.2 /gm.JJ TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch NH.sub.4 HB.sub.2 O.sub.7 (2 wt. % cylindrical extrudates; Catalyst as B.sub.2 O.sub.3) surface area: 146 m.sup.2 /gm.KK TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch NH.sub.4 HB.sub.4 O.sub.7 /WO.sub.3 cylindrical extrudates; Catalyst surface area: 148 m.sup.2 /gm.LL TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch NH.sub.4 HB.sub.4 O.sub.7 /NH.sub.4 VO.sub.3 cylindrical extrudates; Catalyst surface area: 142 m.sup.2 /gm.MM TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch NH.sub.4 HB.sub.4 O.sub.7 /NH.sub.4 VO.sub.3 cylindrical extrudates; Catalyst surface area: 144 m.sup.2 /gm.NN TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch NH.sub.4 HB.sub.4 O.sub.7 /NaVO.sub.3 cylindrical extrudates; Catalyst surface area: 110 m.sup.2 /gm.OO TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch (NH.sub.4) W.sub.12 O.sub.41 cylindrical extrudates; Catalyst surface area: 141 m.sup.2 /gm.PP TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch (NH.sub.4).sub.6 H.sub.2 W.sub.12 O.sub.41 cylindrical extrudates; Catalyst (8 wt. %) surface area: 156 m.sup.2 /gm.QQ TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Na.sub.2 WO.sub.4.9 WO.sub.3 cylindrical extrudates; Catalyst (2 wt. % as WO.sub.3) surface area: 145 m.sup.2 /gm.RR TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch V.sub.2 O.sub.5 cylindrical extrudates; Catalyst surface area: 127 m.sup.2 /gm.SS TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch NaVO.sub.3 (2 wt. %) cylindrical extrudates; Catalyst surface area: 83 m.sup.2 /gm.TT TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch La.sub.2 O.sub.3 /B.sub.2 O.sub.5 /WO.sub.3 cylindrical extrudates; Catalyst surface area: 152 m.sup.2 /gm.UU ZrO.sub.2 /SiO.sub.2 /TiO.sub.2 Particle size: 1/16 inch cylindrical extrudates; Catalyst surface area: 127 m.sup.2 /gm.VV ZrO.sub.2 /SiO.sub.2 / Particle size: 1/16 inch (NH.sub.4).sub.6 H.sub.2 W.sub.12 O.sub.40 cylindrical extrudates; Catalyst (2 wt. % as WO.sub.3) surface area: 120 m.sup.2 /gm.WW TiO.sub.2 (anatase)/ Particle size: 1/16 inch (NH.sub.4).sub.2 HPO.sub.4 cylindrical extrudates; Catalyst surface area: 100 m.sup.2 /gm.XX TiO.sub.2 (rutile)/ Particle size: 1/16 inch (NH.sub.4).sub.2 HPO.sub.4 cylindrical extrudates; Catalyst surface area: 0.34 m.sup.2 /gm.YY TiO.sub.2 (rutile)/ Particle size: 1/16 inch H.sub.3 PO.sub.4 cylindrical extrudates; Catalyst surface area: 1.08 m.sup.2 /gm.ZZ TiO.sub.2 (anatase) Particle size: 1/16 inch cylindrical extrudates; Catalyst surface area: 188.4 m.sup.2 /gm.AAA TiO.sub.2 (anatase)/SiO.sub.2 Particle size: 1/16 inch cylindrical extrudates; Catalyst surface area: 186 m.sup.2 /gm.BBB TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch H.sub.3 BO.sub.3 cylindrical extrudates; Catalyst surface area: 154 m.sup.2 /gm.CCC TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch H.sub.3 VO.sub.4 cylindrical extrudates; Catalyst surface area: 146 m.sup.2 /gm.DDD TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch NH.sub.4 BF.sub.4 /H.sub.3 PO.sub.4 cylindrical extrudates; Catalyst surface area: 94 m.sup.2 /gm.EEE TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch NaBF.sub.4 cylindrical extrudates; Catalyst surface area: 107 m.sup.2 /gm.FFF TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch H.sub.2 B.sub.4 O.sub.7 /H.sub.3 PO.sub.4 cylindrical extrudates; Catalyst surface area: 142 m.sup.2 /gm.GGG TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Nb.sub.2 O.sub.5 cylindrical extrudates; Catalyst surface area: 151 m.sup.2 /gm.HHH TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch ZrO.sub.2 cylindrical extrudates; Catalyst surface area: 151 m.sup.2 /gm.III TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Fe.sub.2 O.sub.3 cylindrical extrudates; Catalyst surface area: 142 m.sup.2 /gm.JJJ TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch SnO cylindrical extrudates; Catalyst surface area: 253 m.sup.2 /gm.KKK TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch H.sub.3 BO.sub.3 /H.sub.3 VO.sub.4 cylindrical extrudates; Catalyst surface area: 152 m.sup.2 /gm.LLL TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Na.sub.2 O cylindrical extrudates; Catalyst surface area: 151 m.sup.2 /gm.MMM TiO.sub.2 (anatase)/SiO.sub. 2 / Particle size: 1/16 inch ZnO cylindrical extrudates; Catalyst surface area: 137 m.sup.2 /gm.NNN TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch La.sub.2 O.sub.3 cylindrical extrudates; Catalyst surface area: 134 m.sup.2 /gm.OOO TiO.sub.2 (anatase)/SiO.sub.2 / Particle size: 1/16 inch Li.sub.2 O cylindrical extrudates; Catalyst surface area: 127 m.sup.2 /gm.PPP TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 Particle size: 1/16 inch cylindrical extrudates; Catalyst surface area: 185 m.sup.2 /gm.QQQ TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch Na.sub.2 O cylindrical extrudates; Catalyst surface area: 117 m.sup.2 /gm.RRR TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch La.sub.2 O.sub.3 cylindrical extrudates; Catalyst surface area: 142 m.sup.2 /gm.SSS TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch La.sub.2 O.sub.3 /H.sub.3 PO.sub.4 cylindrical extrudates; Catalyst surface area: 115 m.sup.2 /gm.TTT TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch MgO cylindrical extrudates; Catalyst surface area: 137 m.sup.2 /gm.UUU TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch Li.sub.2 O cylindrical extrudates; Catalyst surface area: 105 m.sup.2 /gm.VVV TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch NaBF.sub.4 cylindrical extrudates; Catalyst surface area: 138 m.sup.2 /gm.WWW TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch SrO cylindrical extrudates; Catalyst surface area: 141 m.sup.2 /gm.XXX TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch H.sub.3 BO.sub.3 cylindrical extrudates; Catalyst surface area: 159 m.sup.2 /gm.YYY TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch ZnO cylindrical extrudates; Catalyst surface area: 141 m.sup.2 /gm.ZZZ TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch SnO cylindrical extrudates; Catalyst surface area: 125 m.sup.2 /gm.AAAA TiO.sub.2 (anatase)/Al.sub.2 O.sub.3 / Particle size: 1/16 inch Fe.sub.2 O.sub.3 cylindrical extrudates; Catalyst surface area: 147 m.sup.2 /gm.BBBB Titanium dioxide (anatase)/ Particle size: 1/16 inch sodium trimetaphosphate; cylindrical extrudates; Ti:P atom ratio = 5.7:1 Catalyst surface area: 133.3 m.sup.2 /gm; Pore volume N.sub.2 : 0.344 cc/gm; Pore area: 83.5 m.sup.2 /gm; Bulk density: 1.55 gm/cc.CCCC Titanium dioxide (anatase)/ Particle size: 1/16 inch sodium tripolyphosphate; inch cylindrical extrudates; Ti:P atom ratio = 5.7:1 Catalyst surface area: 80.3 m.sup.2 /gm; Pore volume N.sub.2 : 0.236 cc/gm; Pore area: 54.2 m.sup.2 /gm; Bulk density: 1.72 gm/cc.DDDD Titanium dioxide (anatase)/ Particle size: 1/16 inch AB1; Ti:P atom ratio = cylindrical extrudates; 5.7:1 Catalyst surface area: 115.0 m.sup.2 /gm; Pore volume N.sub.2 : 0.429 cc/gm; Pore area: 87.4 m.sup.2 /gm; Bulk density: 1.39 gm/cc.EEEE Titanium dioxide (anatase)/ Particle size: 1/16 inch sodium pyrophosphate; cylindrical extrudates; Ti:P atom ratio = 5.7:1 Catalyst surface area: 78.6 m.sup.2 /gm; Pore volume N.sub.2 : 0.339 cc/gm; Pore area: 72.1 m.sup.2 /gm; Bulk density: 1.59 gm/cc.FFFF Titanium dioxide Particle size: 1/16 inch (anatase)/sodium cylindrical extrudates; dihydrogen phosphate; Catalyst surface area: Ti:P atom ratio = 5.7:1 117.1 m.sup.2 /gm; Pore volume N.sub.2 : 0.321 cc/gm; Pore area: 85.7 m.sup.2 /gm; Bulk density: 1.64 gm/cc.GGGG Titanium dioxide Particle size: 1/16 inch (anatase)/disodium cylindrical extrudates; dihydrogen pyrophosphate; Catalyst surface area: Ti:P atom ratio = 5.7:1 133.5 m.sup.2 /gm; Pore N.sub.2 : 0.291 cc/gm; Pore area: 89.6 m.sup.2 /gm; Bulk density: 1.66 gm/cc.HHHH Titanium dioxide Particle size: 1/16 inch (anatase)/disodium cylindrical extrudates; hydrogen phosphate; Catalyst surface area: Ti:P atom ratio = 5.7:1 117/4 m.sup.2 /gm; Pore volume N.sub.2 : 0.346 cc/gm; Pore area 86.5 m.sup.2 /gm; Bulk density: 1.53 gm/cc.IIII Titanium dioxide Particle size: 1/16 inch (anatase)/sodium cylindrical extrudates: phosphate; Ti:P Catalyst surface area: 88.4 atom ratio = 5.7:1 m.sup.2 /gm; Pore volume N.sub.2 : 0.365 cc/gm; Pore area: 76.90 m.sup.2 /gm; Bulk density: 1.48 gm/cc.__________________________________________________________________________

For each run the tubular reaction system was brought up to the designated conditions. The ammonia feed was established first, then the EDA-MEA, DETA-AEEA or DETA-MEA feed, as appropriate. After a sufficient line out period, a two hour timed run was conducted, then the experiment was run overnight and sampled. The feed was changed to another reactant set and the above procedure repeated.

Performance moderator additions

Diammonium hydrogen phosphate preparation to provide a performance moderator: Catalyst pellets (150 cc) were added to a saturated solution of diammonium hydrogen phosphate in water. Enough solution was added to completely immerse the pellets. The slurry was allowed to stand at a temperature of 55.degree.-60.degree. C. for a period of 8 hours. The catalyst was filtered, washed with water until the wash water was neutral, dried at a temperature of 100.degree. C., and then calcined at a temperature of 600.degree. C. for a period of 6-8 hours.

Hydrogen fluoride preparation to provide a performance moderator: Catalyst pellets (150 cc) were added to a saturated solution of ammonium fluoride in water. Enough solution was added to completely immerse the pellets. The slurry was allowed to stand at a temperature of 55.degree.-60.degree. C. for a period of 8 hours. The catalyst was filtered, washed with water until the wash water was neutral, dried at a temperature of 100.degree. C., and then calcined at a temperature of 600.degree. C. for a period of 6-8 hours.

Sulfuric acid preparation to provide a performance moderator: Catalyst pellets (150 cc) were added to a saturated solution of ammonium sulphate in water. Enough solution was added to completely immerse the pellets. The slurry was allowed to stand at a temperature of 55.degree.-60.degree. C. for a period of 8 hours. The catalyst was filtered, washed with water until the wash water was neutral, dried at a temperature of 100.degree. C., and then calcined at a temperature of 600.degree. C. for a period of 6-8 hours.

Catalyst J Preparation: Tin (II) ethylene glycoxide (9.88 grams) was dissolved in 150 milliliters of monoethanolamine. The resulting solution was diluted with isopropanol (80 milliliters) and the TiO.sub.2 /Al.sub.2 O.sub.3 support (280 grams) was impregnated. The support turned yellow. After a period of 1 hour, the catalyst was filtered and washed with excess isopropanol, dried and then calcined at a temperature of 600.degree. C. for a period of 16 hours. The catalyst was divided into 2 equal parts--one part was used to make Catalyst Q.

Catalyst K Preparation: Boric acid (2.86 grams) was dissolved in just enough water to impregnate the TiO.sub.2 /SiO.sub.2 support (140 grams). The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst L Preparation: The TiO.sub.2 /Al.sub.2 O.sub.3 support (280 grams) was impregnated with niobium pentoxide-toluene solution (13.68 grams of niobium pentoxide). Excess toluene was removed under reduced pressure on a Buchi rotary evaporator. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The catalyst was divided into 2 equal parts. One part was impreqnated with ammonium vanadate (2.83 grams) dissolved in water. This catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The second part was used to make Catalyst O described below.

Catalyst M Preparation: The TiO.sub.2 /SiO.sub.2 support (280 grams) was impreqnated with lanthanum nitrate (7.59 grams) in sufficient water to wet all of the support. The wet catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The catalyst (140 grams) was then soaked in 85% phosphoric acid for a period of 1 hour and washed with water until neutral. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst N Preparation: The TiO.sub.2 /SiO.sub.2 support (280 grams) was impreqnated with lanthanum nitrate (7.59 grams) in sufficient water to wet all of the support. The wet catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst O Preparation: The second part of Catalyst L greenware was impregnated with boric acid (2.86 grams) in sufficient water to wet the support. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst P Preparation: Ammonium vanadate (2.83 grams) was dissolved in sufficient water to impregnate the TiO.sub.2 /SiO.sub.2 support (140 grams). The wet catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst Q Preparation: The second part of Catalyst J greenware was impreqnated with 85% phosphoric acid for a period of 1 hour and then washed with water until neutral. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst R Preparation: The TiO.sub.2 /Al.sub.2 O.sub.3 support was used without further treatment.

Catalyst S Preparation: Tin (II) ethylene glycoxide (9.88 grams) was dissolved in 150 milliliters of monoethanolamine and the TiO.sub.2 /SiO.sub.2 support (280 grams) was impregnated therewith. The TiO.sub.2 /SiO.sub.2 support turned yellow. After a period of 1 hour, the catalyst was filtered and washed with excess isopropanol to remove excess monoethanolamine. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The catalyst was divided into 2 equal parts. One part was impregnated with boric acid (2.86 grams) dissolved in sufficient water to wet the support. This catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The second part was used to make Catalyst X described below.

Catalyst T Preparation: The TiO.sub.2 /Al.sub.2 O.sub.3 support (280 grams) was impregnated with lanthanum nitrate (7.59 grams) in sufficient water to wet the support. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The catalyst was then impregnated with ammonium vanadate (2.83 grams) in sufficient water to wet the support. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst U Preparation: The TiO.sub.2 /SiO.sub.2 support (280 grams) was impregnated with niobium pentoxide in toluene (13.68 grams). Excess toluene was removed under reduced pressure on a Buchi rotary evaporator. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The catalyst was divided into 2 equal parts. One portion was impregnated with 85% phosphoric acid for a period of 1 hour and then washed with water until neutral. The wet catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The second part was used as Catalyst V described below.

Catalyst V Preparation: The second part of Catalyst U prior to impregnation with phosphoric acid was used without further treatment.

Catalyst W Preparation: The TiO.sub.2 /Al.sub.2 O.sub.3 support (280 grams) was impregnated with lanthanum nitrate (7.59 grams) in sufficient water to wet the support. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The catalyst was then impregnated with boric acid (2.86 grams) in sufficient water to wet the support. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst X Preparation: The second part of Catalyst S greenware was impregnated with ammonium vanadate (2.83 grams) in sufficient water to wet the support. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst Y Preparation: The TiO.sub.2 /Al.sub.2 O.sub.3 support (140 grams) was impreqnated with 85% phosphoric acid for a period of 1 hour and then washed with water until neutral. The wet catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst Z Preparation: The TiO.sub.2 /Al.sub.2 O.sub.3 support (280 grams) was impreqnated with lanthanum nitrate (7.59 grams) in sufficient water to wet all of the support. The wet catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. The catalyst (140 grams) was then soaked in 85% phosphoric acid for a period of 1 hour and washed with water until neutral. The catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst AA Preparation: Sodium tetraborate (21 grams) was dissolved in water (112 grams) and used to impregnate the TiO.sub.2 /SiO.sub.2 support (140 grams). After a period of 1 hour, excess liquid was decanted and the material dried at a temperature of 100.degree. C. for a period of 1 hour. The catalyst was then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst BB Preparation: Sodium stannate (21 grams) was dissolved in just enough water (56.4 grams) to impregnate the TiO.sub.2 /SiO.sub.2 support (140 grams). After a period of 1 hour, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst CC Preparation: The ZrO.sub.2 /SiO.sub.2 support was used without further treatment.

Catalyst DD Preparation: A solution of niobium pentethoxide (25.28 grams) in toluene (84.18 grams) was prepared. The ZrO.sub.2 /SiO.sub.2 support (140 grams) was slurried with toluene (75 milliliters) and then the niobium pentethoxide solution (29.6 grams) was added. Excess toluene was removed under reduced pressure and the catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour. The catalyst was then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst EE Preparation: Boric acid (2.86 grams) was dissolved in methanol (75 milliliters) and the ZrO.sub.2 /SiO.sub.2 support (140 grams) was impregnated with this solution. The catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst FF Preparation: Ammonium metavanadate (2.86 grams) was dissolved in water (75 milliliters) and the ZrO.sub.2 /SiO.sub.2 support (140 grams) was impregnated with this solution. The catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst GG Preparation: The TiO.sub.2 /SiO.sub.2 support was used without further treatment.

Catalyst HH Preparation: The TiO.sub.2 /SiO.sub.2 /Al.sub.2 O.sub.3 support was used without further treatment.

Catalyst II Preparation: Boric acid (2.86 grams) was dissolved in just enough water to impregnate the TiO.sub.2 /SiO.sub.2 support (140 grams). The catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and the calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst JJ Preparation: Ammonium hydrogentetraborate (4.19 grams) was dissolved in water (104.3 grams) to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour, the catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst KK Preparation: Ammonium hydrogentetraborate (4.19 grams) and ammonium tungstate (5.89 grams) were dissolved in sufficient water (95.45 grams) to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst LL Preparation: Ammonium hydrogentetraborate (4.19 grams) and ammonium vanadate (5.62 grams) were dissolved in sufficient water (170.2 grams) to dissolve the inorganic salts. The TiO.sub.2 /SiO.sub.2 support (140 grams) was immersed in this solution for a period of 1 hour. Excess liquid was decanted and the catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour. The catalyst was then calcined at a temperature of 600.degree. C. for a period of 16 hours.

Catalyst MM Preparation: Ammonium hydrogentetraborate (4.19 grams) and ammonium vanadate (5.62 grams) were dissolved in sufficient hot water (176 grams). The TiO.sub.2 /SiO.sub.2 support (140 grams) was added to the hot solution, stirred well and then allowed to cool to room temperature. The catalyst slurry was transferred to a round bottom flask and stripped under reduced pressure using a Buchi evaporator. The catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst NN Preparation: Ammonium hydrogentetraborate (4.19 grams) was dissolved in sufficient water (94 grams) to wet the TiO.sub.2/ SiO.sub.2 support (140 grams). After an impregnation period of 1 hour, the catalyst was dried at a temperature of 100.degree. C. and then calcined at a temperature of 400.degree. C. for a period of 16 hours. Sodium vanadate (5.85 grams) was dissolved in water (94 grams) sufficient to wet the calcined material. After an impregnation period of 1 hour, the catalyst was redried at a temperature of 100.degree. C. and calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst OO Preparation: Ammonium metatungstate (3.12 grams) was dissolved in a sufficient amount of water (103 grams) to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). The catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst PP Preparation: Ammonium metatungstate (12.26 grams) was dissolved in a sufficient amount of water (94 grams) to wet the Ti).sub.2 /SiO.sub.2 support (140 grams). The catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst QQ Preparation: Sodium metatungstate (2.86 grams) was dissolved in sufficient water (88.4 grams) to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst RR Preparation: A solution of vanadium triisopropoxide (7.60) grams in toluene (76.85 grams) was prepared and added to the TiO.sub.2 /SiO.sub.2 support (140 grams) in a round bottom flask on a Buchi evaporator. After mixing for a period of 1 hour, excess toluene was removed under reduced pressure and the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst SS Preparation: Sodium vanadate (21 grams) was dissolved in water (84.3 grams). A small amount (2.55 grams) did not dissolve and this was removed by filtration. The solution was poured over the TiO.sub.2 /SiO.sub.2 support with stirring. Excess liquid (14.85 grams) was removed and the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst TT Preparation: Boric acid (2.97 grams), lanthanum nitrate (10.39 grams) and ammonium tungstate (6.13 grams) were dissolved in water (94 grams) and the TiO.sub.2 /SiO.sub.2 support (140 grams) was impregnated with the solution. The catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst UU Preparation: Titanium isopropoxide (10.25 grams) was dissolved in toluene (45.44 grams). This solution was used to impregnate the ZrO.sub.2 /SiO.sub.2 support (140 grams). Excess toluene was removed under reduced pressure. The catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst VV Preparation: Ammonium tungstate (3.12 grams) was dissolved in a sufficient amount of water (63.24 grams) to wet the ZrO.sub.2 /SiO.sub.2 support (140 grams). After impregnation for a period of 1 hour at room temperature, the catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst WW Preparation: Diammonium hydrogen phosphate (65 grams) was dissolved in water (50 grams) in a round bottom flask and anatase TiO.sub.2 (150 cubic centimeters) was added to the flask. The flask was rotated on a Buchi rotary evaporator under reduced pressure for a period of 2 hours. The resulting slurry was filtered, washed with water (100 milliliters) and dried at a temperature of 100.degree. C. for a period of 1 hour and then at a temperature of 250.degree. C. for overnight.

Catalyst XX Preparation: Diammonium hydrogen phosphate (65 grams) was dissolved in water (50 grams) in a round bottom flask and rutile TiO.sub.2 (150 cubic centimeters) was added to the flask. The flask was rotated on a Buchi rotary evaporator under reduced pressure for a period of 2 hours. The resulting slurry was filtered, washed with water (100 milliliters) and dried at a temperature of 100.degree. C. for a period of 1 hour and then at a temperature of 250.degree. C. for overnight.

Catalyst YY Preparation: Orthophosphoric acid (52 grams), water (50 grams) and TiO.sub.2 (171.11 grams) were placed in a flask on a Buchi rotary evaporator at a pressure of 210 millimeters Hg for a period of 2 hours. The catalyst was filtered and washed with distilled water (2500 milliliters) to pH 6, dried at a temperature of 100.degree. C. for a period of 1 hour and then at a temperature of 250.degree. C. for a period of 16 hours. The resulting catalyst (171.11 grams) was slurried with phosphoric acid (52.37 grams) and water (50.05 grams) for a period of 2 hours on a Buchi rotary evaporator at a pressure of 310 mm Hg, filtered, washed with water (100 milliliters), evaporated dry and heated at a temperature of 100.degree. C. for a period of 1 hour and then at a temperature of 250.degree. C. for a period of 16 hours.

Catalyst ZZ Preparation: The TiO.sub.2 support was used without further treatment.

Catalyst AAA Preparation: Obtained from Norton Company, Akron, Ohio.

Catalyst BBB Preparation: Boric acid (1.81 grams) was mixed in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (100 grams). After an impregnation period of 1 hour, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst CCC Preparation: Ammonium vanadate (2.63 grams) was mixed in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst DDD Preparation: Ammonium tetrafluoroborate (8.39 grams) and diammonium hydrogen phosphate (10.52 grams) were dissolved in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst EEE Preparation: Sodium tetrafluoroborate (2.86 grams) was dissolved in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst FFF Preparation: Ammonium hydrogen tetraborate (4.18 grams) and diammonium hydrogen phosphate (10.52 grams) were dissolved in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was dried at a temperature of 100.degree. C. for a period of 8 hours and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst GGG Preparation: Niobium pentoxide (13.67 grams) dissolved in toluene (approximately 200 milliliters) was used to wet the TiO.sub.2 /SiO.sub.2 support (280 grams). After an impregnation period of 15 minutes at room temperature, toluene was removed under reduced pressure and the catalyst was dried at a temperature of 100.degree. C. for a period of 8 hours and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst HHH Preparation: Zirconium n-propoxide (7.59 grams) dissolved in toluene (62 grams) was used to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After standing overnight under a cover at room temperature, the catalyst was stripped under reduced pressure and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst III Preparation: Ferric nitrate. 9H.sub.2 O (7.21 grams) was dissolved in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst JJJ Preparation: Tin (II) acetate (95%) (4.42 grams) was dissolved in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst KKK Preparation: Ammonium hydrogen borate (2.53 grams) and ammonium vanadate (5.62 grams) were dissolved at a temperature of 75.degree. C. in excess water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). The excess water was then evaporated. After an impregnation period of 1 hour, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst LLL Preparation: Sodium bicarbonate (4.15 grams) was dissolved in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (100 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst MMM Preparation: Zinc nitrate hexahydrate (10.44 grams) was dissolved in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst NNN Preparation: Lantanum nitrate hexahydrate (3.79 grams) was dissolved in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst OOO Preparation: Lithium acetate dihydrate (9.74 grams) was dissolved in sufficient water to wet the TiO.sub.2 /SiO.sub.2 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst PPP Preparation: Obtained from Norton Company, Akron, Ohio.

Catalyst QQQ Preparation: Sodium bicarbonate (4.15 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (100 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst RRR Preparation: Lanthanum nitrate hexahydrate (3.79 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst SSS Preparation: Lanthanum nitrate hexahydrate (4.29 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (160 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours. This material (140 grams) was slurried with 85% phosphoric acid (90 milliliters) for a period of 1 hour, filtered, washed with water until pH of 6.5 and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst TTT Preparation: Magnesium nitrate hexahydrate (18.17 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst UUU Preparation: Lithium acetate dihydrate (9.74 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst VVV Preparation: Sodium tetrafluoroborate (2.86 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst WWW Preparation: Strontium nitrate (5.84 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst XXX Preparation: Boric acid (1.81 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (100 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst YYY Preparation: Zinc nitrate hexahydrate (10.44 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst ZZZ Preparation: Stannous acetate (95%) (4.42 grams) was dissolved in hot monoethanolamine diluted with isopropanol (30 grams) and slurried with the TiO support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was dried at a temperature of 100.degree. C. for a period of 1 hour. Excess liquid was then drained off. The catalyst was washed with isopropanol and then calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst AAAA Preparation: Ferric nitrate. 9H.sub.2 O (7.21 grams) was dissolved in sufficient water to wet the TiO.sub.2 /Al.sub.2 O.sub.3 support (140 grams). After an impregnation period of 1 hour at room temperature, the catalyst was calcined at a temperature of 400.degree. C. for a period of 16 hours.

Catalyst BBBB: Obtained from Norton Company, Akron, Ohio.

Catalyst CCCC: Obtained from Norton Company, Akron, Ohio.

Catalyst DDDD: Obtained from Norton Company, Akron, Ohio.

Catalyst EEEE: Obtained from Norton Company, Akron, Ohio.

Catalyst FFFF: Obtained from Norton Company, Akron, Ohio.

Catalyst GGGG: Obtained from Norton Company, Akron, Ohio.

Catalyst HHHH: Obtained from Norton Company, Akron, Ohio.

Catalyst IIII: Obtained from Norton Company, Akron, Ohio.

TABLE I______________________________________Example No. 1 2 3 4 5______________________________________Catalyst Type A A A A ATEMP., .degree.C.; ave. 228 241 290 294 268PRES., psia 1172.7 1214.7 1214.7 1214.7 914.7AEEA SV; M/kg 1.61 1.44 1.5 1.56 0.9cat/hr.EDA/AEEA Mole 1.5 1.5 2 2 5RatioNH.sub.3 /AEEA Mole Ratio 24.2 45.83 34.9 36.33 55.94H.sub.2 O/AEEA Mole Ratio 0.86 0.86 0.66 1.38 1.18Wt % H.sub.2 O 7.4 7.4 5 10 5% Conversion AEEA 70.4 73.2 97 61.8 97.3ANALYTICAL, area %EDA 62.81 65.97 60.95 62.65 77.39MEA 0.92 0.41 0.12 0.13 0PIP 5.52 5.84 9.66 6.36 5.23DETA 2.33 2.58 3.68 1.24 3.49AEEA 15.51 14.19 1.36 17.33 0.7AEP 0.89 1.03 2.13 0.35 2.49HEP 0.17 0.13 0.1 0.14 0.04TETA 5.1 4.45 4.47 1.78 4.64DAEP 1.70 1.77 4.42 3.10 2.00PEEDA 1.99 2.11 5.00 3.02 2.15DPE 0 0.56 0.14 0.19 0.07Total TETAS 8.79 8.38 14.02 8.08 8.91Total TEPAS 0.87 0.77 2.01 0.29 0.96Total Byproducts 2.19 0.72 5.98 3.43 0.79% Water 16.68 21.18 13.75 13.94 10.66______________________________________Example No. 6 7 8 9______________________________________Catalyst Type A A A ATEMP., .degree.C.; ave. 242 247 295 270PRES., psia 1214.7 1214.7 414.7 614.7AEEA SV; M/kg cat/hr. 0.57 0.69 1.18 2.21EDA/AEEA Mole Ratio 8 8 2 0.8NH.sub.3 /AEEA Mole Ratio 107.9 91.22 66.88 30.36H.sub.2 O/AEEA Mole Ratio 3.61 3.61 0.66 0.44Wt % H.sub.2 O 10 10 5 5% Conversion AEEA 43.3 23.3 98.6 27ANALYTICAL, area %EDA 87.72 84.11 60.49 43.42MEA 0 0 0 0PIP 0.68 0.64 11.37 3.72DETA 0 0.13 4.03 0AEEA 9.96 13.57 0.63 49.49HEP 0 0.01 0.1 0.06AEP 0.06 0.05 3.82 0.06TETA 0.40 0.46 3.36 0.20DAEP 0.16 0.16 5.78 1.52PEEDA 0.12 0.10 5.09 1.01DPE 0 0 0.32 --Total TETAS 0.68 0.71 14.26 2.72Total TEPAS 0.22 0.14 1.62 0.04Total Byproducts 0.68 0.64 3.67 0.49% Water 12 9.97 17.34 12.18______________________________________Example No. 10 11 12______________________________________Catalyst Type F G DTemp. .degree.C. 172 178 258Press. psig 614 614.7 614.7Space veloc- 2.2 2.4 2.2ity g mol/kg-cat/hrFeed Comp. EDA/AEEA/ EDA/AEEA/ EDA/AEEA/ NH.sub.3 NH.sub.3 NH.sub.3Feed Mole 2/1/37 2/1/12.5 2/1/10.8Ratio% water; 5 0 5feed% Conv. 40.4 40.7 41.5R.sub.x OutletComp. Area% GGEDA 32.94 46.98 39.1MEA 0.38 0 0.66PIP 0.03 0 8.95DETA 8.03 24.37 1.3AEEA 57.53 27.91 27.01AEP 0.98 0.72 0.85nc-TETA.sup.2 0.02 0 7.96c-TETA.sup.3 0 6.68TEPA's 0.02 0 1.73HPA/ 0.06 0.02 5.55UNKNOWNS______________________________________Example No. 13 14______________________________________Catalyst Type D BTemp. .degree.C. 261 284Press. psig 614.7 614.7Space velocity 3.3 2g mol/kg-cat/hrFeed Comp. DETA/MEA/NH.sub.3 DETA/MEA/NH.sub.3Feed Mole Ratio 2/1/11.9 2/1/10.7% water; feed 5 5% Conv. 34.5(DETA) 66.7R.sub.x Outlet Comp.Area % GGEDA 1.63 1.45MEA 24.16 7.75PIP 0.93 0.77DETA 50.93 75.48AEEA 2.22 0.19AEP 7.76 1.54nc-TETA 8.21 9.67c-TETA 0.89 0.55TEPA's 1.88 1.13HPA/UNKNOWNS 1.35 1.45______________________________________Example No. 15 16 17______________________________________Catalyst Type H E ETemp. .degree.C. 180 268 266Press. psig 614.7 614.7 614.7Space veloc- 3.3 2.4 2.1ity g mol/kg-cat/hrFeed Comp. EDA/AEEA/ EDA/AEEA/ DETA/MEA/ NH.sub.3 NH.sub.3 NH.sub.3Feed Mole 2/1/9.5 2/1/18.5 2/1/16.2Ratio% water; 0 0 0feed% Conv. 23.5 96.2 42.9R.sub.x OutletComp. Area% GGEDA 58.46 43.41 2.32MEA 0.03 0.14 13.14PIP 0.05 16.67 2.28DETA 6.12 5.16 42.38AEEA 35.27 1.74 0.96AEP 0 2.17 8.87nc-TETA.sup.2 0 8.3 14.84c-TETA.sup.3 0 12.17 3.46TEPA's 0 2.61 7.08HPA/ 0.07 7.55 4.48UNKNOWNS______________________________________Example No. 18 19 20______________________________________Catalyst Type C C BTemp. .degree.C. 257 279 259Press. psig 614.7 614.7 614.7Space veloc- 2.4 2.3 2.1ity g mol/kg-cat/hrFeed Comp. DETA/MEA/ DETA/MEA/ EDA/AEEA/ NH.sub.3 NH.sub.3 NH.sub.3Feed Mole 2/1/11.7 2/1/13.2 2/1/10.0Ratio% water; 0 0 5feed% Conv. 45.3 75 21.8R.sub.x OutletComp. Area% GGEDA .56 1.02 44.38MEA 12.7 5.71 0PIP 0.47 1.32 2.25DETA 80.17 78.73 8.92AEEA 0.35 0 37.01AEP 0.84 1.77 0.21nc-TETA.sup.2 3.95 6.43 5.64c-TETA.sup.3 0.17 0.55 0.58TEPA's 0.34 0.93 0.45HPA/ 0.4 3.04 0.47UNKNOWNS______________________________________Example No. 21 22______________________________________Catalyst Type I CTemp. .degree.C. 179 274Press. psig 614.7 614.7Space velocity 2.4 4.7g mol/kg-cat/hrFeed Comp. EDA/AEEA/NH.sub.3 EDA/MEA/NH.sub.3Feed Mole Ratio 2/1/11.1 1/1/5.3% water; feed 0 0% Conv. 42.3 42R.sub.x Outlet Comp.Area % GGEDA 61.7 56.03MEA 0 29.12PIP 0 1.83DETA 10.43 4.58AEEA 25.84 1.44AEP 0.5 1.92nc-TETA 0 1.00c-TETA 0 0.99TEPA's 0 0.53HPA/UNKNOWNS 1.53 2.54______________________________________ .sup.2 nc = noncyclics .sup.3 c = cyclics TABLE II__________________________________________________________________________Example No. 23 24 25 26 27 28 29 30 31__________________________________________________________________________Catalyst Type J J J J J J J J JCatalyst weight, gm 81.0 81.0 81.0 81.0 81.0 81.0 81.0 81.0 81.0Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.7 269.5 280.7 260.2 270.9 258.8 279.7 268.7 268.9Time on organics, hrs. 25.0 27.0 30.0 47.5 53.0 72.5 78.5 96.0 104.0Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.65 4.99 5.19 4.45 4.75 3.91 4.36 4.43 4.87NH.sub.3 feedrate, gm/hr 40.6 43.8 46.3 36.7 38.6 30.9 35.8 38.5 42.3Liquid feed composition, wt. %DETA 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81MEA 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19Liquid product composition,wt. %EDA 1.06 0.96 1.65 0.58 0.93 0.44 1.29 0.76 0.71MeEDA 0 0 0 0 0 0 0 0 0MEA 27.97 29.69 25.97 33.84 31.26 33.34 25.75 31.85 32.53EtEDA 0 0 0 0 0 0 0 0 0PIP 0.41 0.35 0.65 0.13 0.26 0.09 0.38 0.15 0.12DETA 48.20 49.21 45.95 52.63 51.53 56.05 49.30 52.04 53.16AEEA 3.81 4.35 3.82 3.19 4.30 2.48 4.17 3.47 3.39AEP 0.47 0.36 0.67 0.22 0.30 0.17 0.47 0.26 0.25HEP 0 0 0 0 0 0 0 0 0TETA's 10.10 8.61 10.77 5.04 7.01 3.88 9.98 5.75 4.72TEPA's 3.39 1.88 3.55 0.11 0.82 0 2.63 0.63 0.44MEA Conversion % 22.93 17.73 26.84 5.52 13.89 7.65 28.09 10.64 8.96Acyclic (N4)/cyclic (< = N4), 43.8 46.8 41.4 100 119 AL 32.1 80.5 ALweight ratioAcyclic (N5)/cyclic (< = N5), 19.5 AL 60.6 AL AL -- AL 0.2 ACweight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.26 0.17 0.25 0.02 0.09 0 0.20 0.08 0.07weight ratio__________________________________________________________________________ AL = All linear AC = All cyclic TABLE III__________________________________________________________________________Example No. 32 33 34 35 36 37 38 39 40 41 42 43__________________________________________________________________________Catalyst Type K K K K K K K K K K K KCatalyst weight, gm 69.8 86.2 69.8 86.2 69.8 86.2 69.8 69.8 69.8 69.8 69.8 69.8Pressure, psig 600 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.0 269.9 270.1 269.8 280.3 280.8 260.0 270.4 260.6 280.7 270.0 270.5Time on organics, hrs. 7.0 25.0 28.2 27.0 32.0 30.0 51.0 55.5 76.0 80.0 98.0 100.0Duration of run, hrs. 2 2 2.2 2 2 2 2 2 1 1 2 2MEA SV, gmol/hr/kgcat 6.58 4.13 5.83 4.39 6.07 3.45 5.23 1.85 5.05 5.44 5.46 5.60NH.sub.3 feedrate, gm/hr 57.2 38.4 52.1 41.1 48.5 32.7 40.3 15.1 19.8 21.6 44.6 46.2Liquid feed composition, wt. %DETA 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81MEA 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19Liquid product composition,wt. %EDA 1.24 1.60 0.95 1.21 1.43 1.80 0.74 0.74 0.74 1.34 0.74 0.87MeEDA 0 0 0 0 0 0 0 0 0 0 0 0MEA 19.67 22.54 26.20 25.34 19.49 20.13 29.73 29.73 29.73 23.12 28.77 29.57EtEDA 0 0 0 0 0 0 0 0 0 0 0 0PIP 0.65 1.03 0.53 0.72 0.93 1.19 0.38 0.38 0.38 0.86 0.40 0.44DETA 55.44 45.02 50.44 47.30 46.80 44.02 51.65 51.65 51.65 48.33 52.65 50.62AEEA 2.25 3.72 4.05 4.52 2.91 3.70 3.10 3.10 3.10 2.98 3.53 3.82AEP 0.70 1.12 0.49 0.69 1.01 1.09 0.37 0.37 0.37 0.82 0.34 0.38HEP 0 0 0 0 0 0 0 0 0 0 0 0TETA's 9.65 11.96 9.66 10.63 12.87 13.06 6.39 6.39 6.39 11.07 7.31 6.58TEPA's 4.85 6.85 2.52 3.79 7.21 6.64 1.70 1.70 1.70 5.04 0.69 1.22MEA Conversion % 46.11 37.81 27.53 29.68 45.85 43.35 16.29 16.29 16.29 35.76 19.42 16.21Acyclic (N4)/cyclic (< = N4), 27.7 12.2 32.7 35.6 21.4 23.5 29.0 29.0 54.2 21.4 24.9 26.3weight ratioAcyclic (N5)/cyclic (< = N5), 24.3 16.4 AL 42.8 14.0 17.2 AL AL 1.0 22.0 1.2 4.0weight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.39 0.44 0.20 0.28 0.43 0.39 0.21 0.21 0.21 0.35 0.07 0.14weight ratio__________________________________________________________________________ AL = All linear TABLE IV__________________________________________________________________________Example No. 44 45 46 47 48 49 50 51 52__________________________________________________________________________Catalyst Type L L L L L L L L LCatalyst weight, gm 81.0 81.0 81.0 81.0 81.0 81.0 81.0 81.0 81.0Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 280.0 260.0 270.0 261.1 281.0 270.0 271.1 280.8Time on organics, hrs. 5.5 8.5 25.5 30.5 49.0 55.0 63.0 65.0 83.5Duration of run, hrs. 1 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.82 2.44 5.36 5.37 5.39 5.95 5.42 5.82 5.02NH.sub.3 feedrate, gm/hr 21.8 22.1 55.8 54.8 55.0 69.9 57.3 61.5 56.6Liquid feed composition, wt. %DETA 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81MEA 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19Liquid product composition,wt. %EDA 2.69 2.69 1.29 1.35 1.28 3.69 2.47 2.35 4.26MeEDA 0 0 0 0 0 0 0 0 0MEA 26.60 26.60 35.62 32.63 34.35 25.96 31.23 30.52 27.27EtEDA 0 0 0 0 0 0 0 0 0PIP 0.37 0.37 0.08 0.14 0.05 0.19 0.09 0.08 0.14DETA 47.58 47.58 53.88 52.05 56.50 53.83 57.32 55.41 53.05AEEA 2.60 2.60 1.47 1.73 1.17 1.43 1.35 1.26 1.21AEP 0.43 0.43 0.20 0.26 0.19 0.38 0.27 0.27 0.44HEP 0 0 0 0 0 0 0 0 0TETA's 10.73 10.73 3.22 5.26 1.92 6.33 1.69 2.44 3.03TEPA's 1.91 1.91 0 0.28 0 0.67 0 1.71 1.16MEA Conversion % 24.56 24.56 0.03 6.94 3.40 25.65 11.47 13.43 19.76Acyclic (N4)/cyclic (< = N4), 151.7 21.9 14.4 19.4 7.9 25.5 3.0 5.5 4.7weight ratioAcyclic (N5)/cyclic (< = N5), 4.0 7.9 -- 2.1 -- 1.2 -- 1.4 1.6weight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.14 0.13 0 0.04 0 0.08 0 0.54 0.30weight ratio__________________________________________________________________________ TABLE V__________________________________________________________________________Example No. 53 54 55 56 57 58 59 60 61__________________________________________________________________________Catalyst Type M M M M M M M M MCatalyst weight, gm 85.2 85.2 85.2 85.2 85.2 85.2 85.2 85.2 85.2Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 280.0 260.0 270.0 260.8 280.5 270.0 271.1 280.3Time on organics, hrs. 5.5 8.5 25.5 30.5 49.0 55.0 63.0 65.0 83.5Duration of run, hrs. 1 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 5.28 5.07 5.48 5.84 5.52 6.52 5.81 6.13 5.44NH.sub.3 feedrate, gm/hr 24.7 48.6 56.6 61.3 58.5 58.5 62.6 66.0 62.2Liquid feed composition, wt. %DETA 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81MEA 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19Liquid product composition,wt. %EDA 1.32 2.15 0.85 1.26 0.90 2.02 1.37 1.38 2.33MeEDA 0 0 0 0 0 0 0 0 0MEA 15.57 10.16 24.66 18.69 22.60 8.57 15.60 15.52 7.94EtEDA 0 0 0 0 0 0 0 0 0PIP 1.21 1.79 0.67 1.08 0.67 1.48 1.10 1.14 1.74DETA 41.58 39.29 46.91 43.53 49.14 40.82 44.78 45.27 38.44AEEA 2.20 1.15 2.85 2.14 2.98 0.66 1.62 1.56 0.56AEP 1.22 1.98 0.54 1.04 0.61 1.67 1.07 1.11 1.93HEP 0 0 0 0 0 0 0 0 0TETA's 16.72 18.77 11.96 15.23 12.45 17.75 16.10 16.16 17.53TEPA's 11.40 12.43 4.91 8.93 4.19 15.36 10.78 10.47 17.18MEA Conversion % 56.69 71.01 31.16 47.92 37.24 75.81 57.10 57.41 77.50Acyclic (N4)/cyclic (< = N4), 28.1 10.7 39.8 27.5 58.3 10.0 28.4 20.2 7.7weight ratioAcyclic (N5)/cyclic (< = N5), 17.8 11.1 AL 28.1 AL 9.6 20.8 20.2 7.7weight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.53 0.51 0.32 0.45 0.26 0.67 0.52 0.50 0.76weight ratio__________________________________________________________________________ AL = All linear TABLE VI__________________________________________________________________________Example No. 62 63 64 65 66 67 68 69 70__________________________________________________________________________Catalyst Type N N N N N N N N NCatalyst weight, gm 77.8 77.8 77.8 77.8 77.8 77.8 77.8 77.8 77.8Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 270.0 280.0 260.0 270.0 260.0 280.0 270.0 270.0Time on organics, hrs. 5.7 24.0 29.9 46.7 50.7 70.0 73.2 94.5 96.2Duration of run, hrs. 1 2 2 2 2 2 1 1.5 1.5AEEA SV, gmol/hr/kgcat 6.67 4.63 4.91 3.59 2.96 2.58 3.91 3.41 3.48NH.sub.3 feedrate, gm/hr 21.8 50.0 46.9 32.5 28.0 23.2 18.2 22.2 22.7Liquid feed composition, wt. %DETA 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76AEEA 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24Liquid product composition,wt. %EDA 0.44 0.39 0.77 0.24 0.48 0.24 0.87 0.49 0.48MeEDA 0 0 0 0 0 0 0 0 0MEA 0.09 0 0.08 0 0 0 0.07 0.08 0.08EtEDA 0 0 0 0 0 0 0 0 0PIP 4.44 4.13 5.87 3.20 4.67 3.53 6.10 4.40 4.40DETA 43.18 42.76 43.32 44.28 43.52 42.38 42.49 42.87 42.71AEEA 26.48 26.78 16.71 37.36 26.70 34.34 16.74 27.84 28.30AEP 0.39 0.35 0.55 0.17 0.36 0.18 0.54 0.34 0.32HEP 0 0 0 0 0 0 0 0 0TETA's 3.69 4.01 5.95 1.76 3.48 2.16 5.38 3.50 3.11TEPA's 15.71 15.98 19.62 9.10 14.81 12.31 18.59 13.57 13.51AEEA Conversion % 45.75 45.11 65.52 23.95 45.05 29.69 64.66 42.02 40.92Acyclic (N4)/cyclic (< = N4), 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1weight ratioAcyclic (N5)/cyclic (< = N5), 34.1 27.3 26.5 28.9 32.0 5.2 31.0 31.9 38.4.SIGMA.(N5)/.SIGMA.(N4), 4.3 4.0 3.3 5.2 4.3 5.7 3.5 3.9 4.3weight ratio__________________________________________________________________________ TABLE VII__________________________________________________________________________Example No. 71 72 73 74 75 76 77 78 79__________________________________________________________________________Catalyst Type O O O O O O O O OCatalyst weight, gm 79.2 79.2 79.2 79.2 79.2 79.2 79.2 79.2 79.2Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 270.0 283.0 258.0 270.9 260.0 280.8 270.3 270.9Time on organics, hrs. 5.5 24.0 29.5 48.2 54.0 72.0 77.0 96.0 98.0Duration of run, hrs. 2 2 1 2.2 2 2 2 2 2AEEA SV, gmol/hr/kgcat -- -- -- -- -- -- -- -- --NH.sub.3 feedrate, gm/hr 23.9 44.4 23.5 60.7 63.0 38.0 50.5 43.3 42.4Liquid feed composition, wt. %DETA 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76AEEA 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24Liquid product composition,wt. %EDA 0.72 0.52 1.19 0.21 0.27 0 0.86 0.49 0.45MeEDA 0 0 0 0 0 0 0 0 0MEA 0.18 0 0.10 0 0 0 0.12 0.07 0.08EtEDA 0 0 0 0 0 0 0 0 0PIP 3.26 3.37 5.01 1.95 2.53 1.91 4.25 3.00 2.84DETA 44.51 41.52 43.07 43.76 42.61 42.89 43.51 44.61 43.96AEEA 21.05 28.04 18.66 41.43 34.60 41.04 22.86 32.99 33.50AEP 0.51 0.40 0.69 0.17 0.30 0.17 0.46 0.30 0.30HEP 0 0 0 0 0 0 0 0 0TETA's 4.12 3.89 5.55 1.56 2.66 1.64 4.87 2.56 2.65TEPA's 16.72 15.50 16.20 6.95 11.77 8.80 15.08 9.19 10.75AEEA Conversion % 55.29 41.70 60.26 15.17 28.72 16.50 51.95 30.81 30.79Acyclic (N4)/cyclic (< = N4), 0.1 0.2 0.2 0.2 0.1 0.2 0.2 0.1 0.1weight ratioAcyclic (N5)/cyclic (< = N5), 21.9 28.0 18.9 18.8 35.8 32.4 25.2 26.1 16.9weight ratio.SIGMA.(N5)/.SIGMA.(N4), 4.1 4.0 2.9 4.5 4.4 3.1 3.1 3.6 4.1weight ratio__________________________________________________________________________ TABLE VIII__________________________________________________________________________Example No. 80 81 82 83 84 85 86 87 88__________________________________________________________________________Catalyst Type P P P P P P P P PCatalyst weight, gm 70.3 70.3 70.3 70.3 70.3 70.3 70.3 70.3 70.3Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 270.0 280.0 260.0 270.0 260.0 280.8 270.6 269.0Time on organics, hrs. 5.5 22.5 29.0 52.0 54.5 72.2 78.0 96.5 98.5Duration of run, hrs. 2 1 2 1 1 2 2 2 2AEEA SV, gmol/hr/kgcat -- -- -- -- -- -- -- -- --NH.sub.3 feedrate, gm/hr 21.6 14.3 32.8 30.7 29.8 50.4 43.6 38.0 38.9Liquid feed composition, wt. %DETA 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76AEEA 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24Liquid product composition,wt. %EDA 2.46 1.29 1.46 0.41 0.59 0.36 0.24 0.75 0.70MeEDA 0 0 0 0 0 0 0 0 0MEA 1.52 0.91 0.77 0.43 0.40 0.21 0.22 0.23 0.17EtEDA 0 0 0 0 0 0 0 0 0PIP 4.80 3.83 4.36 2.11 2.78 2.01 4.12 3.40 3.25DETA 37.58 41.15 42.68 44.21 41.99 43.58 39.66 43.51 41.45AEEA 16.78 26.05 23.62 42.66 33.98 43.20 23.91 34.37 33.86AEP 1.48 0.54 0.55 0.14 0.31 0.14 0.42 0.29 0.20HEP 0 0 0 0 0 0 0 0 0TETA's 7.37 3.99 3.66 0.85 2.68 1.01 4.52 2.37 2.61TEPA's 16.17 14.01 13.88 5.45 10.84 5.68 18.03 9.38 10.95AEEA Conversion % 63.30 44.80 49.70 12.60 29.00 11.50 49.67 28.70 29.10Acyclic (N4)/cyclic (< = N4), 0.9 0.3 0.1 0.1 0.1 0.3 0.1 0.1 0.1weight ratioAcyclic (N5)/cyclic (< = N5), 11.8 20.5 23.8 22.6 22.9 24.2 13.2 30.5 18.2weight ratio.SIGMA.(N5)/.SIGMA.(N4), 2.2 3.5 3.8 6.4 4.0 5.6 4.0 4.0 4.2weight ratio__________________________________________________________________________ TABLE IX__________________________________________________________________________Example No. 89 90 91 92 93 94 95 96 97__________________________________________________________________________Catalyst Type Q Q Q Q Q Q Q Q QCatalyst weight, gm 92.4 92.4 92.4 92.4 92.4 92.4 92.4 92.4 92.4Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 270.0 280.0 260.0 270.0 260.0 280.0 270.0 270.0Time on organics, hrs. 5.7 24.0 29.0 46.7 50.7 70.0 73.2 94.5 96.2Duration of run, hrs. 1 2 2 2 2 2 1 1.5 1.5AEEA SV, gmol/hr/kgcat -- -- -- -- -- -- -- -- --NH.sub.3 feedrate, gm/hr 20.7 54.6 46.1 39.5 43.8 36.2 19.9 23.6 24.5Liquid feed composition, wt. %DETA 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76AEEA 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24Liquid product composition,wt. %EDA 0.62 0.77 1.43 0.35 0.65 0.34 1.54 0.85 0.85MeEDA 0 0 0 0 0 0 0 0 0MEA 0.05 0.05 0.12 0 0 0 0.12 0.05 0.05EtEDA 0 0 0 0 0 0 0 0 0PIP 5.03 5.21 6.86 3.37 4.62 3.56 6.78 5 4.91DETA 41.13 41.09 41.25 41.84 41.18 42.24 40.18 40.78 40.48AEEA 22.03 21.43 12.01 33.20 23.91 32.48 12.42 22.88 23.37AEP 0.50 0.51 1.00 0.32 0.47 0.32 0.94 0.49 0.47HEP 0 0 0 0 0 0 0 0 0TETA's 4.09 4.42 6.08 2.05 3.98 1.87 4.49 3.99 3.92TEPA's 20.24 20.45 22.65 14.14 19.44 13.37 20.88 18.77 18.49AEEA Conversion % 54.80 56.17 74.97 32.22 51.14 32.91 72.86 52.54 51.35Acyclic (N4)/cyclic (< = N4), 0.2 0.2 0.2 0.2 0.2 0.2 0.3 0.2 0.2weight ratioAcyclic (N5)/cyclic (< = N5), 37.8 37.9 37.9 28.4 39.5 22.2 22.3 40.8 36.2weight ratio.SIGMA.(N5)/.SIGMA.(N4), 5.0 4.6 4.6 6.9 4.9 7.2 4.7 4.7 4.7weight ratio__________________________________________________________________________ TABLE X__________________________________________________________________________Example No. 98 99 100 101 102 103 104 105 106__________________________________________________________________________Catalyst Type R R R R R R R R RCatalyst weight, gm 83.0 83.0 83.0 83.0 83.0 83.0 83.0 83.0 83.0Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.3 269.2 280.3 260.0 270.7 258.8 279.4 268.6 268.9Time on organics, hrs. 25.0 27.0 30.0 47.5 53.0 72.5 78.5 96.0 104.0Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.36 5.83 4.87 4.24 4.63 4.25 4.23 4.49 4.84NH.sub.3 feedrate, gm/hr 3.93 42.6 44.5 35.7 38.8 34.3 35.5 39.3 42.8Liquid feed composition, wt. %DETA 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81MEA 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19Liquid product composition,wt. %EDA 1.48 1.57 2.02 0.69 1.06 0.53 1.45 0.83 0.78MeEDA 0 0 0 0 0 0 0 0 0MEA 22.85 29.24 17.65 29.77 25.97 31.82 20.10 27.71 29.07EtEDA 0 0 0 0 0 0 0 0 0PIP 0.64 0.66 0.94 0.22 0.41 0.15 0.60 0.26 0.23DETA 45.36 55.10 42.59 50.64 49.02 53.67 45.37 50.33 50.69AEEA 4.02 5.66 3.65 4.36 4.97 3.75 4.15 4.75 4.55AEP 0.79 0.77 1.15 0.28 0.45 0.23 0.79 0.79 0.30HEP 0 0 0 0 0 0 0 0 0TETA's 12.73 15.31 14.61 7.65 9.90 5.99 13.50 8.57 7.66TEPA's 5.73 6.96 8.41 1.55 2.93 0.37 6.56 2.11 1.74MEA Conversion % 36.63 34.01 50.31 17.19 28.09 12.29 43.92 23.51 19.12Acyclic (N4)/cyclic (< = N4), 26.3 37 19.1 59.2 49.2 73.5 30.6 56.3 91.8weight ratioAcyclic (N5)/cyclic (< = N5), 16.6 26.7 17.3 AL AL Al 16.1 AL ALweight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.35 0.35 0.44 0.16 0.23 0.05 0.38 0.19 0.18weight ratio__________________________________________________________________________ AL = All linear TABLE XI__________________________________________________________________________Example No. 107 108 109 110 111 112 113 114 115__________________________________________________________________________Catalyst Type S S S S S S S S SCatalyst weight, gm 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 280.0 260.0 270.0 260.0 280.2 270.0 270.8 279.6Time on organics, hrs. 5.5 8.5 25.5 30.5 49.0 55.0 63.0 65.0 83.5Duration of run, hrs. 1 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.98 3.19 5.17 5.40 4.94 5.17 2.91 3.20 2.01NH.sub.3 feedrate, gm/hr 23.8 22.8 28.4 28.8 26.7 31.6 16.1 17.5 11.7Liquid feed composition, wt. %DETA 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81AEEA 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19Liquid product composition,wt. %EDA 1.41 2.05 0.56 0.87 0.58 1.66 1.73 1.61 3.20MeEDA 0 0 0 0 0 0 0 0 0MEA 19.33 14.89 32.59 28.88 30.91 19.92 22.47 22.59 14.36EtEDA 0 0 0 0 0 0 0 0 0PIP 0.90 1.42 0.34 0.61 0.30 1.17 1.29 1.22 2.55DETA 52.52 49.03 53.57 50.73 55.21 50.05 49.40 49.57 40.30AEEA 3.10 2.24 2.82 3.11 2.59 2.54 2.81 2.84 1.84AEP 0.85 1.56 0.26 0.44 0.23 1.07 0.95 0.90 2.16HEP 0 0 0 0 0 0 0 0 0TETA's 9.47 11.11 5.40 8.10 5.43 11.41 10.18 10.98 13.32TEPA's 5.10 7.91 0.97 2.28 0.46 5.29 4.71 5.15 11.87MEA Conversion % 46.07 57.87 10.12 19.83 14.19 44.75 37.61 38.21 59.43Acyclic (N4)/cyclic (< = N4), 27.7 11.6 29.1 31.2 29.4 19.7 18.6 24.8 5.9weight ratioAcyclic (N5)/cyclic (< = N5), 24.3 7.9 3.8 AL 0.5 12.4 13.9 20.6 8.8weight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.42 0.55 0.14 0.22 0.07 0.36 0.36 0,.36 0.69weight ratio__________________________________________________________________________ AL = All linear TABLE XII__________________________________________________________________________Example No. 116 117 118 119 120 121 122 123 124Catalyst Type T T T T T T T T T__________________________________________________________________________Catalyst weight, gm 70.3 70.3 70.3 70.3 70.3 70.3 70.3 70.3 70.3Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.6 269.8 280.0 260.0 269.9 259.9 280.0 270.0 269.8Time on organics, hrs. 7.0 28.2 32.0 51.0 55.5 76.0 80.0 98.0 100.0Duration of run, hrs. 2 2.2 2 2 2 1 1 2 2MEA SV, gmol/hr/kgcat 6.41 5.47 5.54 5.55 5.99 4.94 4.87 5.13 5.09NH.sub.3 feedrate, gm/hr 57.0 50.0 47.4 42.9 51.0 19.5 20.2 42.8 42.6Liquid feed composition, wt. %DETA 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81MEA 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19Liquid product composition, wt. %EDA 1.76 1.72 2.79 1.20 1.54 1.03 3.28 1.62 1.77MeEDA 0 0 0 0 0 0 0 0 0MEA 28.93 31.18 25.30 34.17 32.94 36.96 29.76 34.70 34.76EtEDA 0 0 0 0 0 0 0 0 0PIP 0.31 0.20 0.35 0.11 0.13 0.05 0.26 0.08 0.08DETA 51.86 51.84 47.27 52.54 50.53 55.52 49.86 54.14 52.26AEEA 2.46 2.38 2.35 1.71 1.94 1.39 2.21 1.69 1.72AEP 0.34 0.26 0.43 0.27 0.22 0.18 0.37 0.23 0.23HEP 0 0 0 0 0 0 0 0 0TETA's 8.21 6.88 8.88 4.83 4.02 0.75 6.01 1.23 2.76TEPA's 1.20 0.40 1.93 0.61 0.28 0 0.77 0.75 0.69MEA Conversion % 19.48 12.50 25.30 4.19 3.61 3.96 14.28 1.23 0.93Acyclic (N4)/cyclic (< = N4), 61.5 34.2 29.6 8.2 10.8 5.2 15.9 5.1 10.0weight ratioAcyclic (N5)/cyclic (< = N5), 8.7 2.5 6.9 3.1 1.0 -- 1.6 0.8 0.9weight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.11 0.04 0.18 0.10 0.05 0.00 0.10 0.47 0.19weight ratio__________________________________________________________________________ TABLE XIII__________________________________________________________________________Example No. 125 126 127 128 129 130 131 132 133Catalyst Type U U U U U U U U U__________________________________________________________________________Catalyst weight, gm 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.2 270.6 280.0 260.0 270.6 260.3 280.3 270.0 270.4Time on organics, hrs. 7.0 28.2 32.0 51.0 55.5 76.0 80.0 98.0 100.0Duration of run, hrs. 2 2.2 2 2 2 1 1 2 2MEA SV, gmol/hr/kgcat 5.80 5.38 5.30 5.18 5.59 4.76 4.64 4.77 4.93NH.sub.3 feedrate, gm/hr 58.1 55.5 50.5 45.4 52.8 21.4 21.7 44.7 46.5Liquid feed composition, wt. %DETA 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81 62.81MEA 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19 37.19Liquid product composition, wt. %EDA 1.49 1.58 2.41 1.49 1.60 1.33 3.12 1.81 1.94MeEDA 0 0 0 0 0 0 0 0 0MEA 15.80 15.60 7.88 21.06 16.72 23.31 8.72 16.63 16.40EtEDA 0 0 0 0 0 0 0 0 0PIP 1.24 1.29 1.79 1.18 1.30 1.03 2.25 1.45 1.52DETA 43.99 41.88 35.04 44.83 41.24 45.12 38.12 42.49 42.23AEEA 1.68 1.76 0.69 2.11 1.79 2.59 0.65 1.94 1.78AEP 1.28 1.32 2.09 1.44 1.21 0.82 2.32 1.36 1.42HEP 0 0 0 0 0 0 0 0 0TETA's 16.06 16.67 18.12 12.97 15.56 12.51 17.44 15.73 15.55TEPA's 10.63 11.12 17.85 7.24 9.80 5.36 14.78 9.38 9.35MEA Conversion % 56.44 56.59 77.25 41.21 52.29 34.25 75.14 53.32 53.67Acyclic (N4)/cyclic (< = N4), 45.2 22.5 7.5 21.2 22.4 34.8 8.8 23.5 22.7weight ratioAcyclic (N5)/cyclic (< = N5), 22.8 18.1 7.8 16.0 18.1 30.1 9.5 16.3 16.1weight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.51 0.52 0.76 0.43 0.48 0.33 0.65 0.46 0.46weight ratio__________________________________________________________________________ TABLE XIV__________________________________________________________________________Example No. 134 135 136 137 138 139 140 141 142Catalyst Type V V V V V V V V V__________________________________________________________________________Catalyst weight, gm 73.7 73.7 73.7 73.7 73.7 73.7 73.7 73.7 73.7Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 270.0 280.0 260.0 270.0 260.0 280.0 270.7 270.0Time on organics, hrs. 5.5 22.5 29.0 52.0 54.5 72.2 78.0 96.5 98.5Duration of run, hrs. 2 1 2 1 1 2 2 2 2AEEA SV, gmol/hr/kgcat 6.67 4.63 4.91 3.59 2.96 2.58 3.91 3.41 3.48NH.sub.3 feedrate, gm/hr 23.9 9.9 48.8 23.5 28.5 31.0 25.0 26.9 26.3Liquid feed composition, wt. %DETA 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76AEEA 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24Liquid product composition, wt. %EDA 1.79 1.51 1.41 0.34 0.50 0.35 1.70 0.78 0.74MeEDA 0 0 0 0 0 0 0 0 0MEA 1.07 1.17 0.74 0.25 0.33 0.24 0.04 0.16 0.15EtEDA 0 0 0 0 0 0 0 0 0PIP 5.52 3.76 5.76 2.81 3.63 3.64 6.92 5.05 4.86DETA 35.90 41.93 41.57 41.16 41.76 42.48 39.49 41.16 39.75AEEA 12.93 27.03 18.11 36.99 28.20 33.45 13.29 23.75 23.90AEP 1.55 0.45 0.89 0.18 0.37 0.30 0.97 0.44 0.40HEP 0 0 0 0 0 0 0 0 0TETA's 8.53 3.5 6.04 2.12 3.43 2.57 7.05 4.24 3.96TEPA's 20.89 12.30 16.43 11.31 14.45 12.09 20.16 16.39 16.70AEEA Conversion % 71.98 42.53 61.68 24.04 40.94 31.50 71.70 50.18 49.03Acyclic (N4)/cyclic (< = N4), 0.6 0.3 0.3 0.1 0.1 0.1 0.2 0.1 0.1weight ratioAcyclic (N5)/cyclic (< = N5), 11.5 23.0 21.5 29.0 36.6 40.9 21.5 38.7 40.6weight ratio.SIGMA.(N5)/.SIGMA.(N4), 2.4 3.5 2.7 5.3 4.2 4.7 2.9 3.9 4.2weight ratio__________________________________________________________________________ TABLE XV__________________________________________________________________________Example No. 143 144 145 146 147 148 149 150 151Catalyst Type W W W W W W W W W__________________________________________________________________________Catalyst weight, gm 73.4 73.4 73.4 73.4 73.4 73.4 73.4 73.4 73.4Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 270.0 283.0 258.0 270.9 260.0 280.8 270.3 270.9Time on organics, hrs. 6.0 24.0 29.5 48.2 54.0 72.0 77.0 96.0 98.0Duration of run, hrs. 2 2 1 2.2 2 2 2 2 2AEEA SV, gmol/hr/kgcat -- -- -- -- -- -- -- -- --NH.sub.3 feedrate, gm/hr 49.4 47.0 25.3 63.8 66.2 40.9 55.0 45.8 45.5Liquid feed composition, wt. %DETA 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76AEEA 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24Liquid product composition, wt. %EDA 0.59 0.51 1.22 0.19 0.25 0.17 0.76 0.44 0.45MeEDA 0 0 0 0 0 0 0 0 0MEA 0.20 0.07 0.09 0 0 0 0.12 0.07 0.07EtEDA 0 0 0 0 0 0 0 0 0PIP 2.85 3.05 4.72 1.66 2.14 1.61 3.58 2.65 2.63DETA 45.65 41.32 44.05 44.34 42.13 42.52 43.04 44.85 44.90AEEA 24.65 30.56 20.44 43.92 36.81 42.99 25.69 25.38 36.09AEP 0.44 0.40 0.82 0.17 0.31 0.16 0.51 0.32 0.31HEP 0 0 0 0 0 0 0 0 0TETA's 3.12 2.96 4.96 0.73 1.76 0.98 4.05 1.48 1.46TEPA's 14.38 15.11 15.08 6.05 11.07 7.67 15.97 8.80 8.72AEEA Conversion % 47.86 36.83 56.81 10.83 23.78 12.00 46.91 40.95 25.27Acyclic (N4)/cyclic (< = N4), 0.2 0.2 0.3 0.1 0.1 0.2 0.2 0.1 0.1weight ratioAcyclic (N5)/cyclic (< = N5), 29.2 29.9 16.2 33.1 34.6 30.5 23.6 23.1 24.5weight ratio.SIGMA.(N5)/.SIGMA.(N4), 4.6 5.1 3.0 8.3 6.3 7.8 3.9 6.0 6.0weight ratio__________________________________________________________________________ TABLE XVI__________________________________________________________________________Example No. 152 153 154 155 156 157 158 159 160Catalyst Type X X X X X X X X X__________________________________________________________________________Catalyst weight, gm 84.4 84.4 84.4 84.4 84.4 84.4 84.4 84.4 84.4Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 270.0 280.0 260.0 270.0 260.0 280.8 270.6 270.0Time on organics, hrs. 5.5 22.5 29.0 52.0 54.5 72.2 78.0 96.5 98.5Duration of run, hrs. 2 1 2 1 1 2 2 2 2AEEA SV, gmol/hr/kgcat -- -- -- -- -- -- -- -- --NH.sub.3 feedrate, gm/hr 22.1 22.5 49.2 28.0 28.5 49.7 46.8 44.6 47.7Liquid feed composition, wt. %DETA 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76AEEA 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24Liquid product composition, wt. %EDA 2.27 4.55 1.74 0.58 0.94 0.50 1.87 1.19 0.98MeEDA 0 0 0 0 0 0 0 0 0MEA 1.91 0.49 0.96 0.60 0.48 0.27 0.22 0.28 0.28EtEDA 0 0 0 0 0 0 0 0 0PIP 4.38 8.82 4.05 1.76 2.73 1.76 4.35 3.33 3.06DETA 38.78 30.56 43.07 43.47 43.02 41.40 40.62 43.07 43.67AEEA 18.03 6.55 25.13 44.40 34.37 41.62 22.92 33.81 36.22AEP 1.04 3.42 0.47 0.13 0.29 0.13 0.45 0.29 0.20HEP 0 0 0 0 0 0 0 0 0TETA's 6.08 12.34 3.31 0.97 2.18 1.33 4.49 1.70 2.15TEPA's 15.92 19.32 12.10 4.88 8.78 6.37 13.97 9.45 8.66AEEA Conversion % 60.54 85.60 46.11 9.39 27.39 12.20 50.03 28.95 25.46Acyclic (N4)/cyclic (< = N4), 0.6 0.4 0.1 0.5 0.3 0.4 0.1 0.4 0.3weight ratioAcyclic (N5)/cyclic (< = N5), 11.7 4.9 20.9 19.5 28.4 21.5 8.5 25.7 24.0weight ratio.SIGMA.(N5)/.SIGMA.(N4), 2.6 1.6 3.7 5.0 4.0 4.8 3.1 3.1 4.0weight ratio__________________________________________________________________________ TABLE XVII__________________________________________________________________________Example No. 161 162 163 164 165 166 167 168 169Catalyst Type Y Y Y Y Y Y Y Y Y__________________________________________________________________________Catalyst weight, gm 78.3 78.3 78.3 78.3 78.3 78.3 78.3 78.3 78.3Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 270.0 283.0 258.0 270.9 260.0 280.8 270.3 270.9Time on organics, hrs. 6.0 24.0 29.5 48.2 54.0 72.0 77.0 96.0 98.0Duration of run, hrs. 2 2 1 2.2 2 2 2 2 2AEEA SV, gmol/hr/kgcat -- -- -- -- -- -- -- -- --NH.sub.3 feedrate, gm/hr 47.8 42.9 23.8 60.8 63.8 38.3 51.1 44.1 43.5Liquid feed composition, wt. %DETA 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76AEEA 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24Liquid product composition, wt. %EDA 1.79 0.84 2.05 0.26 0.49 0.27 1.47 0.88 0.81MeEDA 0 0 0 0 0 0 0 0 0MEA 0.07 0.08 0.15 0 0 0 0.13 0.12 0.12EtEDA 0 0 0 0 0 0 0 0 0PIP 5.48 5.20 7.62 3.16 4.17 3.14 6.53 5.51 5.21DETA 40.75 39.06 40.46 42.44 41.21 41.62 39.57 44.13 42.64AEEA 21.03 20.82 10.49 34.11 26.14 34.43 12.94 23.33 23.17AEP 0.61 0.59 1.43 0.32 0.45 0.31 1.03 0.58 0.53HEP 0 0 0 0 0 0 0 0 0TETA's 4.60 5.02 7.77 1.84 3.81 2.33 7.05 3.48 3.34TEPA's 19.42 20.43 18.20 12.67 16.32 13.13 21.97 15.04 14.97AEEA Conversion % 56.84 56.59 77.33 29.89 45.43 29.60 72.79 51.60 50.71Acyclic (N4)/cyclic (< = N4), 0.2 0.2 0.3 0.1 0.2 0.2 0.3 0.1 0.1weight ratioAcyclic (N5)/cyclic (< = N5), 30.5 30.6 14.2 41.1 35.1 47.8 18.1 25.1 25.8weight ratio.SIGMA.(N5)/.SIGMA.(N4), 4.2 4.1 2.3 6.9 4.3 5.6 3.1 4.3 4.5weight ratio__________________________________________________________________________ TABLE XVIII__________________________________________________________________________Example No. 170 171 172 173 174 175 176 177 178Catalyst Type Z Z Z Z Z Z Z Z Z__________________________________________________________________________Catalyst weight, gm 84.8 84.8 84.8 84.8 84.8 84.8 84.8 84.8 84.8Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.0 270.0 280.0 260.0 270.0 260.0 280.0 270.0 270.0Time on organics, hrs. 5.7 24.0 29.0 46.7 50.7 70.0 73.2 94.5 96.2Duration of run, hrs. 1 2 2 2 2 2 1 1.5 1.5AEEA SV, gmol/hr/kgcat -- -- -- -- -- -- -- -- --NH.sub.3 feedrate, gm/hr 23.3 50.0 45.6 37.3 41.3 34.5 19.1 23.4 23.3Liquid feed composition, wt. %DETA 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76 49.76AEEA 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24 50.24Liquid product composition, wt. %EDA 0.46 0.56 1.34 0.26 0.50 0.25 1.36 0.64 0.65MeEDA 0 0 0 0 0 0 0 0 0MEA 0 0.09 0.11 0 0 0 0.09 0 0EtEDA 0 0 0 0 0 0 0 0 0PIP 4.46 4.64 6.90 3.48 4.69 3.53 8.83 4.93 4.96DETA 38.35 39.67 40.51 42.49 41.05 41.84 39.34 40.20 40.66AEEA 21.70 22.16 12.36 33.12 23.84 32.81 12.26 22.74 23.22AEP 0.54 0.54 1.08 0.35 0.51 0.36 1.06 0.54 0.53HEP 0 0 0 0 0 0 0 0 0TETA's 4.66 4.54 5.86 1.96 4.12 1.95 6.78 4.09 3.94TEPA's 22.98 21.35 22.56 13.30 18.84 13.34 21.88 19.39 18.23AEEA Conversion % 55.33 54.49 74.09 32.14 50.92 32.17 74.60 52.73 51.51Acyclic (N4)/cyclic (< = N4), 0.2 0.2 0 0.2 0.2 0.1 0.2 0.2 0.2weight ratioAcyclic (N5)/cyclic (< = N5), 33.9 27.1 19.1 18.8 36.7 14.2 18.5 32.2 36.5weight ratio.SIGMA.(N5)/.SIGMA.(N4), 4.9 4.7 3.9 4.5 4.6 6.8 3.2 4.7 4.6weight ratio__________________________________________________________________________ TABLE XIX__________________________________________________________________________Example No. 179 180 181 182 183 184 185 186Catalyst Type AA AA AA AA AA AA AA AA__________________________________________________________________________Catalyst weight, gm 127.9 127.9 127.9 127.9 127.9 127.9 127.9 127.9Pressure, psig 600 600 600 600 600 600 600 600Temperature, .degree.C. 252.8 252.5 252.8 273.3 271.5 274.3 273.8 273.3Time on organics, hrs. 3.5 18.0 20.0 42.0 44.5 51.5 66.4 68.5Duration of run, hrs. 2 14.5 2 16.5 2.5 2 14.8 2.1MEA SV, gmol/hr/kgcat 1.82 1.81 1.82 1.75 1.79 1.39 1.52 1.63NH.sub.3 feedrate, gm/hr 49.0 59.9 59.9 50.7 48.4 55.0 48.0 67.5Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 -- -- --AEEA -- -- -- -- -- 33.54 33.54 33.54Liquid product composition, wt. %EDA 0.44 0 0 0.57 0.56 0.53 0.55 0.64MeEDA 0 0 0 0 0 0 0 0MEA 19.06 20.36 20.38 16.79 17.14 1.82 0 0EtEDA 0 0 0 0 0 0 0 0PIP 0.35 0.17 0.13 0.55 0.56 5.29 5.83 6.16DETA 73.70 76.19 77.06 74.38 74.02 70.73 66.69 69.84AEEA 0 0 0 0 0 5.43 8.01 8.11AEP 0.35 0.27 0.25 0.62 0.63 0.79 0.58 0.60HEP 0 0 0 0 0 0 0 0TETA's 3.10 3.40 1.18 3.97 3.94 3.94 4.98 4.71TEPA's 0.75 0 0 0.92 0.97 6.54 8.17 8.30ROH Conversion % 15.38 11.83 10.33 25.88 24.31 83.30 75.45 76.02Acyclic (N4)/cyclic (< = N4), AL AL AL 23.21 23.20 0.32 0.11 0.12weight ratioAcyclic (N5)/cyclic (< = N5), AL -- -- AL AL 12.43 18.50 41.50weight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.24 0 0 0.23 0.24 -- -- --weight ratio__________________________________________________________________________ AL = All linear TABLE XX__________________________________________________________________________Example No. 187 188 189 190 191 192 193 194Catalyst Type BB BB BB BB BB BB BB AA__________________________________________________________________________Catalyst weight, gm 125.7 125.7 125.7 125.7 125.7 125.7 125.7 125.7Pressure, psig 600 600 600 600 600 600 600 600Temperature, .degree.C. 260.8 260.0 280.5 280.5 281.5 281.3 279.8 260.5Time on organics, hrs. 16.7 18.7 24.1 41.1 48.1 64.8 66.8 88.7Duration of run, hrs. 15.7 2 2 16.7 2 15.8 2 15.7MEA SV, gmol/hr/kgcat 1.77 2.02 1.77 1.76 1.77 1.63 1.62 1.60NH.sub.3 feedrate, gm/hr 58.2 55.5 49.0 52.7 49.0 52.5 54.5 60.0Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 77.16MEA 22.84 22.84 22.84 22.84 22.84 -- -- 22.84AEEA -- -- -- -- -- 33.54 33.54 --Liquid product composition, wt. %EDA 0 0 1.64 1.13 1.40 2.21 2.12 0MeEDA 0 0 0 0 0 0 0 0MEA 24.27 24.79 18.55 15.91 20.12 0 0 29.98EtEDA 0 0 0 0 0 0 0 0PIP 0.48 0.31 1.35 1.37 1.20 7.44 6.49 0.49DETA 71.40 72.05 67.88 71.46 67.32 70.71 71.20 66.77AEEA 0 0 0 0 0 0 0 0AEP 0.34 0.32 1.14 1.08 0.98 1.10 1.08 0.25HEP 0 0 0 0 0 0 0 0TETA's 2.39 2.45 5.92 5.54 5.28 6.49 5.66 0.44TEPA's 0.93 0 2.51 2.18 2.79 11.91 12.44 0.99ROH Conversion % 6.29 8.67 19.20 30.97 12.19 100.00 100.00 0Acyclic (N4)/cyclic (< = N4), AL AL 8.42 8.58 8.53 0.23 0.25 3.97weight ratioAcyclic (N5)/cyclic (< = N5), AL -- 4.53 AL 6.19 10.77 11.11 ALweight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.39 0 0.42 0.39 0.53 -- -- 2.25weight ratio__________________________________________________________________________ AL = All linear TABLE XXI__________________________________________________________________________Example No. 195 196 197 198 199Catalyst Type CC CC CC CC CC__________________________________________________________________________Catalyst weight, gm 132.3 132.3 132.3 132.3 132.3Pressure, psig 600 600 600 600 600Temperature, .degree.C. 255.5 253.5 253.3 277.3 276.3Time on organics, hrs. 5.5 22.2 24.2 29.7 46.5Duration of run, hrs. 2 15.4 2 1.2 16MEA SV, gmol/hr/kgcat 1.76 1.79 1.80 3.05 1.80NH.sub.3 feedrate, gm/hr 56 53 58 80 57.9Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16MEA 22.84 22.84 22.84 22.84 22.84Liquid product composition, wt. %EDA 0.72 0.57 0.61 4.72 5.56MeEDA 0 0 0 0 0MEA 19.39 18.82 18.97 10.58 10.88EtEDA 0 0 0 0 0PIP 0.58 0.75 0.78 4.57 5.28DETA 74.48 72.48 73.22 60.61 57.25AEEA 1.14 0.55 0 0 0AEP 0.59 0.73 0.75 4.56 5.02HEP 0 0 0 0 0TETA's 3.51 4.43 4.30 8.20 8.44TEPA's 0.74 1.50 1.20 4.98 5.47ROH Conversion % 16.90 18.49 17.80 54.71 53.33Acyclic (N4)/cyclic (< = N4), AL 14.38 14.15 1.84 1.69weight ratioAcyclic (N5)/cyclic (< = N5), AL AL AL 1.17 1.13weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- --weight ratio__________________________________________________________________________ AL = All linear AC = All cyclic TABLE XXII__________________________________________________________________________Example No. 200 201 202 203 204 205 206 207 208 209 210 211__________________________________________________________________________Catalyst Type DD DD DD DD DD DD DD DD DD DD DD DD__________________________________________________________________________Catalyst weight, gm 119.0 119.0 119.0 119.0 119.0 119.0 119.0 119.0 119.0 119.0 119.0 119.0Pressure, psig 600 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 256.8 262.3 258.5 277.3 280.8 280.8 280.8 255.8 274.8 280.3 280.0 259.0Time on organics, hrs. 4.5 20.5 22.5 27.5 35.5 57.0 59.0 80.5 87.5 104.5 106.5 111.5Duration of run, hrs. 2 16 2 2 1.5 21 2 20.7 2 16 2 2MEA SV, gmol/hr/kgcat 1.77 1.92 1.93 1.93 1.92 1.67 1.60 1.71 1.64 1.66 1.72 1.90NH.sub.3 feedrate, gm/hr 70.0 65.8 53.0 61.5 50.6 55.5 51.0 55.1 57 56.1 58 74.5Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 -- -- -- -- -- -- --AEEA -- -- -- -- -- 33.54 33.54 33.54 33.54 33.54 33.54 33.54Liquid product composition,wt. %EDA 0.44 0.46 0.48 2.39 5.14 4.62 4.73 0.69 3.82 4.27 4.42 0.75MeEDA 0 0 0 0 0 0 0 0 0 0 0 0MEA 17.17 16.69 16.56 11.29 8.13 0.93 0 0.35 0 0 0 18.51EtEDA 0 0 0 0 0 0 0 0 0 0 0 0PIP 0.62 0.74 0.75 2.63 4.42 9.83 10.45 5.60 9.71 10.22 10.06 1.17DETA 71.04 70.74 70.92 64.82 58.99 58.30 57.95 64.75 60.92 58.93 58.24 68.48AEEA 0.48 0.48 0.48 0.48 0.48 0.48 0.48 9.57 0 0 0 0.52AEP 0.60 0.70 0.71 2.82 4.88 3.71 3.66 0.61 3.10 3.40 3.52 0.94HEP 0 0 0 0 0 0 0 0 0 0 0 0TETA's 5.44 5.34 6.10 9.66 10.38 9.60 9.73 4.33 9.27 10.07 10.19 6.01TEPA's 1.89 2.14 2.19 4.62 5.30 8.66 9.12 11.34 8.91 8.88 9.52 3.26ROH Conversion % 24.22 26.14 27.45 51.68 65.20 100.00 98.57 71.43 100.0 100.0 100.0 20.00Acyclic (N4)/cyclic AL 20.27 18.61 2.93 2.23 0.39 0.33 0.13 0.30 0.33 0.38 9.99(< = N4),weight ratioAcyclic (N5)/cyclic AL AL AL 2.51 1.23 1.67 1.62 27.57 1.85 1.65 1.72 4.18(< = N5),weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- -- -- -- -- -- --weight ratio__________________________________________________________________________ AL = All linear TABLE XXIII__________________________________________________________________________Example No. 212 213 214 215 216 217 218 219 220 221Catalyst Type EE EE EE EE EE EE EE EE EE EE__________________________________________________________________________Catalyst weight, gm 117.0 117.0 117.0 117.0 117.0 117.0 117.0 117.0 117.0 117.0Pressure, psig 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 263.3 264.5 264.5 282.3 283.0 283.8 283.3 277.5 282.8 262.8Time on organics, hrs. 15 17 17 23 39 41 45 63.5 65.5 70.5Duration of run, hrs. 14 2 2 2 15 2 2 17.5 2 2MEA SV, gmol/hr/kgcat 1.80 1.87 1.68 1.74 1.82 1.76 1.60 1.57 1.58 1.66NH.sub.3 feedrate, gm/hr 69.3 61.0 61.0 107.5 66.8 61.5 62.0 53.2 60.5 70Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- --AEEA -- -- -- -- -- -- 33.54 33.54 33.54 33.54Liquid product composition,wt. %EDA 0.34 0.33 0.31 1.45 1.71 1.75 2.27 2.48 2.68 0.50MeEDA 0 0 0 0 0 0 0 0 0 0MEA 19.00 19.14 18.85 13.73 13.66 13.73 1.37 0.78 0.82 0.68EtEDA 0 0 0 0 0 0 0 0 0 0PIP 0.45 0.45 0.44 1.77 2.06 2.14 6.70 6.85 7.15 3.66DETA 74.32 74.61 74.55 69.65 68.47 68.83 64.69 61.15 60.88 66.11AEEA 0.76 0.67 0.71 0.35 0.33 0.29 2.61 2.71 2.64 15.68AEP 0.51 0.49 0.51 2.02 2.23 2.30 2.23 2.42 2.52 0.46HEP 0 0 0 0 0 0 0.09 0.10 0.11 0.10TETA's 3.45 3.22 3.39 6.74 6.78 6.65 7.65 8.09 8.08 5.03TEPA's 1.05 0.96 1.09 3.63 3.95 3.89 9.99 10.75 10.78 7.59ROH Conversion % 17.59 16.93 18.24 41.12 41.39 41.33 92.30 91.79 92.00 53.98Acryclic (N4)/cyclic (< = N4), 30.61 34.71 19.41 20.90 3.06 3.12 0.32 0.29 0.31 0.60weight ratioAcryclic (N5)/cyclic (< = N5), AL AL AL 1.83 1.60 1.53 1.98 1.79 1.77 19.83weight ratio.SIGMA.(N5)/.SIGMA.(N4), 0.30 0.30 0.32 0.54 0.58 0.50 -- -- -- --weight ratio__________________________________________________________________________ Al = All linear TABLE XXIV__________________________________________________________________________Example No. 222 223 224 225 226 227 228 229 230 231Catalyst Type FF FF FF FF FF FF FF FF FF FF__________________________________________________________________________Catalyst weight, gm 119.4 119.4 119.4 119.4 119.4 119.4 119.4 119.4 119.4 119.4Pressure, psig 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 232.8 230.0 231.8 248.5 244.0 247.3 248.8 250.5 249.5 230.3Time on organics, hrs. 4.0 19.7 22.2 27.1 43.7 45.7 51.0 68.0 70 93Duration of run, hrs. 2 15.7 2.6 2.2 15.7 2 2 16 2 21MEA SV, gmol/hr/kgcat 1.95 1.85 1.96 1.68 1.71 1.79 1.54 1.49 1.64 1.63NH.sub.3 feedrate, gm/hr 59.0 52.1 74.8 63.8 54.2 65.5 54.0 55.6 59 73Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- --AEEA -- -- -- -- -- -- 33.54 33.54 33.54 33.54Liquid product composition,wt. %EDA 1.32 1.44 1.38 4.97 4.71 4.33 3.75 4.12 4.10 0.88MeEDA 0 0 0 0 0 0 0 0 0 0MEA 22.49 22.38 23.57 16.24 15.26 16.13 0.96 0.79 0.89 0.46EtEDA 0 0 0 0 0 0 0 0 0 0PIP 0.15 0.16 0.15 0.66 0.70 0.68 4.48 4.55 4.47 1.85DETA 71.90 71.93 72.75 66.24 65.86 67.79 65.70 65.25 63.53 66.74AEEA 0 0 0 0 0 0 7.29 6.78 7.30 23.94AEP 0.30 0.29 0.28 0.71 0.71 0.73 0.85 1.01 0.83 0.27HEP 0 0 0 0 0 0 0 0 0 0TETA's 1.74 1.84 1.76 4.20 4.28 4.17 4.03 4.23 4.21 1.31TEPA's 0 0 0 1.02 1.00 1.02 5.49 5.53 6.01 3.03ROH Conversion % 0.60 0.05 3.44 24.99 28.48 26.24 76.87 78.43 76.53 28.00Acryclic (N4)/cyclic (< = N4), AL AL AL 9.42 10.16 9.87 0.41 0.41 0.40 0.49weight ratioAcryclic (N5)/cyclic (< = N5), -- -- -- 3.61 3.28 3.95 11.99 12.16 7.62 ALweight ratio.SIGMA.(N5)/.SIGMA.(N4), 0 0 0 0.24 0.23 0.24 -- -- -- --weight ratio__________________________________________________________________________ AL = All linear TABLE XXV__________________________________________________________________________Example No. 232 233 234 235 236 237 238 239 240Catalyst Type GG GG GG GG GG GG GG GG GG__________________________________________________________________________Catalyst weight, gm 71.7 71.7 71.7 71.7 71.7 71.7 71.7 71.7 71.7Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270 270 280 260 270 260 280 270 269.4Time on organics, hrs. 5.5 24.0 29.5 48.5 53.5 72.0 77.5 93.0 94.0Duration of run, hrs. 2 2 2 2 2 2 2 1 1MEA SV, gmol/hr/kgcat 4.14 4.46 4.36 5.52 4.51 4.41 4.26 4.15 4.18DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 1.411 2.048 2.803 0.721 0.985 0.509 2.082 1.210 1.044MEA 16.945 15.112 10.441 24.560 21.874 32.907 18.277 27.514 28.346PIP 1.144 1.466 1.969 0.566 0.916 0.444 1.962 1.108 1.004DETA 51.236 51.808 51.005 56.963 56.336 50.564 48.639 48.512 49.317AEEA 1.633 0.750 0.471 2.854 1.334 3.313 0.761 3.022 2.993AEP 1.408 1.792 2.383 0.570 0.907 0.527 2.313 1.179 1.053HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.906 1.541 1.048 0.803 0.704 0.531 0.684 0.714 0.7121-TETA 10.823 10.188 9.970 6.179 6.720 4.624 7.721 6.104 5.767DAEP 0.338 0.535 0.797 0.105 0.195 0.111 0.723 0.309 0.262PEEDA 0.223 0.461 0.644 0.087 0.173 0.000 0.675 0.341 0.227DPE 0.000 0.000 0.111 0.000 0.000 0.000 0.110 0.067 0.000AE-TAEA 1.379 1.180 1.543 0.441 0.741 0.374 1.397 0.543 0.4621-TEPA 4.588 3.926 4.570 1.388 1.867 0.952 3.120 2.724 1.606AE-DAEP 0.244 0.289 0.620 0.000 0.100 0.000 0.570 0.111 0.092AE-PEEDA 0.105 0.109 0.209 0.000 0.00 0.00 0.260 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.173 0.272 0.386 0.000 0.073 0.000 0.000 0.121 0.081Others 0.204 1.075 1.532 0.612 0.554 0.444 1.746 1.371 1.233MEA Conversion, % 53.39 58.54 71.07 33.10 39.32 8.35 48.80 23.43 21.10DETA Conversion, % 16.24 15.52 16.01 7.78 7.12 16.31 19.02 19.77 18.42Acyclic (N4), % 95.43 92.18 87.66 97.32 95.28 97.90 84.79 90.50 92.98Acrylic (N5), % 91.95 88.40 83.42 100.00 93.78 100.00 84.48 90.71 92.29.SIGMA. (N5)/.SIGMA.(N4), 0.53 0.45 0.58 0.25 0.36 0.25 0.54 0.33 0.32weight ratioAcrylic (N4)/cyclic 3.77 2.76 1.87 5.26 3.39 4.77 1.45 2.27 2.54(< = N4), weight ratio__________________________________________________________________________ TABLE XXVI__________________________________________________________________________Example No. 241 242 243 244 245 246 247 248 249Catalyst Type HH HH HH HH HH HH HH HH HH__________________________________________________________________________Catalyst weight, gm 73 73 73 73 73 73 73 73 73Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 267.3 271.6 280.4 260.3 269.1 261.9 278.4 268.9 268.5Time on organics, hrs. 6.5 25.5 30.5 49.5 54.5 73.5 78.5 97.0 99.2Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.79 3.55 3.59 3.31 3.30 3.15 3.16 2.93 3.01DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 1.819 1.510 2.684 0.504 0.224 0.583 2.338 1.353 1.183MEA 19.544 21.769 15.677 27.977 25.881 29.371 18.842 24.539 25.072PIP 2.131 1.958 2.907 0.791 1.591 0.810 2.955 1.830 1.645DETA 50.736 54.179 44.864 59.947 57.394 60.159 52.360 57.664 58.300AEEA 1.308 1.561 0.890 1.790 1.759 1.755 1.156 1.824 1.888AEP 2.087 1.610 2.837 0.614 0.959 0.559 2.442 1.151 1.012HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.474 0.468 0.382 0.280 0.349 0.222 0.415 0.272 0.2941-TETA 7.326 7.199 7.828 4.424 5.292 3.705 7.135 5.363 5.018DAEP 0.724 0.483 1.000 0.210 0.231 0.161 0.542 0.359 9.292PEEDA 0.625 0.332 1.108 0.086 0.180 0.101 0.599 0.000 0.173DPE 0.419 0.000 0.165 0.000 0.000 0.000 0.000 0.161 0.000AE-TAEA 0.941 0.687 1.356 0.000 0.305 0.000 0.786 1.117 0.2871-TEPA 3.854 2.896 4.945 0.160 0.979 0.000 3.242 0.000 0.839AE-DAEP 0.454 0.209 0.781 0.000 0.000 0.000 0.386 0.000 0.000AE-PEEDA 0.243 0.101 1.082 0.000 0.000 0.000 0.209 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.138 0.000 0.372 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.000 0.648 0.000 0.000 0.000 0.000 0.656 0.000Others 1.377 0.788 3.906 0.418 0.685 0.294 1.783 0.000 0.667MEA Conversion, % 47.04 41.40 57.92 24.31 30.19 20.72 49.47 33.74 32.35DETA Conversion, % 18.29 13.32 28.42 3.61 7.99 3.49 16.55 7.46 6.51Acyclic (N4), % 81.52 90.39 78.32 94.08 93.21 93.74 86.87 91.55 91.94Acrylic (N5), % 85.16 92.04 68.62 100.00 100.00 0.00 87.13 62.99 100.00.SIGMA. (N5)/.SIGMA.(N4), 0.59 0.46 0.88 0.03 0.21 0.00 0.53 0.29 0.19weight ratioAcrylic (N4)/cyclic 1.30 1.75 1.02 2.77 1.91 2.41 1.15 1.61 1.70(< = N4), weight ratio__________________________________________________________________________ TABLE XXVII__________________________________________________________________________Example No. 250 251 252 253 254 255 256 257 258Catalyst Type II II II II II II II II II__________________________________________________________________________Catalyst weight, gm 81.2 81.2 81.2 81.2 81.2 81.2 81.2 81.2 81.2Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 274.4 274.4 280.9 259.8 270.6 259.9 281.6 270.4 270.4Time on organics, hrs. 22.0 26.0 45.5 50.5 69.0 74.5 95.0 119.0 120.0Duration of run, hrs. 2 2 2 2 2 2 2 1 1MEA SV, gmol/hr/kgcat 2.91 2.63 2.50 2.66 2.59 2.54 1.88 5.74 2.90DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.736 1.042 2.004 0.059 0.914 0.285 2.016 0.695 0.525MEA 21.968 25.193 18.576 29.894 25.669 27.372 16.604 25.555 23.517PIP 0.596 0.702 1.478 0.343 0.603 0.232 1.461 0.441 0.380DETA 56.344 55.631 51.168 57.632 56.035 63.408 49.886 55.967 57.620AEEA 3.232 3.031 2.286 2.679 3.151 1.296 2.181 2.896 3.070AEP 0.919 0.802 1.485 0.437 0.730 0.367 1.549 0.662 0.582HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.205 1.108 1.349 0.407 0.739 0.402 1.529 0.684 0.6041-TETA 7.587 6.573 10.443 4.085 6.496 2.782 9.613 6.122 6.727DAEP 0.164 0.130 0.275 0.056 0.100 0.000 0.490 0.102 0.089PEEDA 0.116 0.097 0.252 0.036 0.072 0.138 0.496 0.074 0.057DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 0.283 0.253 0.369 0.000 0.132 0.000 0.958 0.123 0.1731-TEPA 0.935 0.989 2.771 0.078 0.737 0.000 3.253 0.664 0.581AE-DAEP 0.000 0.000 0.161 0.000 0.000 0.000 0.196 0.075 0.000AE-PEEDA 0.000 0.000 0.125 0.000 0.000 0.000 0.156 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 0.666 0.639 1.229 1.336 0.741 0.467 2.672 0.616 0.819MEA Conversion, % 39.80 31.57 49.29 18.66 30.14 25.57 54.52 29.35 35.28DETA Conversion, % 8.23 10.19 16.98 6.80 9.36 2.48 18.80 8.04 5.76Acyclic (N4), % 96.92 97.13 95.72 98.01 97.29 93.00 91.57 96.87 97.18Acrylic (N5), % 100.00 100.00 91.66 100.00 100.00 0.00 92.28 91.26 100.00.SIGMA. (N5)/.SIGMA.(N4), 0.13 0.16 0.28 0.02 0.12 0.00 0.38 0.12 0.10weight ratioAcrylic (N4)/cyclic 4.90 4.44 3.38 5.16 4.71 3.80 2.76 5.14 6.24(< = N4), weight ratio__________________________________________________________________________ TABLE XXVIII__________________________________________________________________________Example No. 259 260 261 262 263 264 265 266 267Catalyst Type JJ JJ JJ JJ JJ JJ JJ JJ JJ__________________________________________________________________________Catalyst weight, gm 70.6 70.6 70.6 70.6 70.6 70.6 70.6 70.6 70.6Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 267.9 267.8 277.8 259.9 270.1 259.9 280.1 269.6 269Time on organics, hrs. 5.0 7.5 26.0 31.5 50.0 55.5 74.0 78.0 80.0Duration of run, hrs. 1 1 2 2 2 2 2 2 1.5MEA SV, gmol/hr/kgcat 7.43 7.71 3.55 3.61 3.27 3.62 3.67 3.54 3.54DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.791 0.623 1.276 0.399 0.923 0.398 1.559 0.813 0.864MEA 26.509 30.058 23.663 33.991 28.444 31.796 22.061 26.996 27.146PIP 1.147 0.517 1.058 0.224 0.638 0.217 1.106 0.510 0.513DETA 47.682 54.106 51.834 56.779 55.100 57.812 53.839 55.907 56.086AEEA 0.876 3.177 3.108 1.987 3.003 2.067 1.970 2.801 2.726AEP 1.015 0.506 1.073 0.246 0.586 0.243 0.935 0.458 0.457HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.944 0.557 0.833 0.309 0.576 0.340 0.831 0.577 0.5721-TETA 9.028 4.870 7.412 2.839 4.781 2.784 7.153 4.597 4.540DAEP 0.183 0.000 0.187 0.000 0.086 0.000 0.082 0.095 0.087PEEDA 0.136 0.000 0.165 0.000 0.000 0.000 0.169 0.000 0.069DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 1.392 0.209 0.543 0.000 0.357 0.119 0.545 0.238 0.2281-TEPA 2.723 0.634 2.000 0.109 0.910 0.179 1.995 0.719 0.686AE-DAEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.194 0.000 0.000Others 0.293 0.493 0.939 0.196 0.758 0.426 1.662 0.989 1.025MEA Conversion, % 26.38 17.06 34.61 6.67 22.13 12.36 39.22 25.04 24.86DETA Conversion, % 21.30 11.27 14.88 7.35 10.35 5.30 11.85 7.74 7.73Acyclic (N4), % 97.18 100.00 95.91 100.00 98.42 100.00 96.96 98.19 97.03Acrylic (N5), % 100.00 100.00 100.00 100.00 100.00 100.00 92.92 100.00 100.00.SIGMA. (N5)/.SIGMA.(N4), 0.36 0.16 0.30 0.03 0.23 0.10 0.33 0.18 0.17weight ratioAcrylic (N4)/cyclic 4.42 5.30 3.32 6.42 4.09 6.79 3.48 4.87 4.54(< = N4), weight ratio__________________________________________________________________________ TABLE XXIX__________________________________________________________________________Example No. 268 269 270 271 272 273 274 275 276Catalyst Type KK KK KK KK KK KK KK KK KK__________________________________________________________________________Catalyst weight, gm 75.7 75.7 75.7 75.7 75.7 75.7 75.7 75.7 75.7Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.6 272.7 279.9 260.3 268.3 261.4 278.9 270.6 271.7Time on organics, hrs. 7.5 26.0 31.0 47.0 53.0 58.5 73.0 78.0 80.0Duration of run, hrs. 2 2 2 2 2 2.5 2 2 2MEA SV, gmol/hr/kgcat 3.78 3.60 4.14 2.88 4.21 4.57 4.11 4.29 4.20DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 1.512 2.957 2.611 0.873 1.230 0.581 2.105 1.136 1.147MEA 19.636 15.858 13.674 24.751 22.713 28.289 17.328 24.549 24.295PIP 0.850 1.545 1.281 0.362 0.559 0.213 0.983 0.499 0.466DETA 53.823 48.802 49.039 57.674 55.152 58.393 51.571 56.716 56.142AEEA 1.077 0.809 1.020 2.059 1.793 1.783 1.230 1.886 1.876AEP 0.980 2.034 1.569 0.409 0.641 0.321 1.189 0.550 0.582HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.511 1.463 1.689 0.877 1.037 0.668 1.665 0.917 0.9521-TETA 9.931 10.166 10.473 6.953 8.198 5.375 10.489 7.020 7.339DAEP 0.209 0.694 0.560 0.075 0.134 0.000 0.248 0.095 0.105PEEDA 0.118 0.559 0.497 0.000 0.091 0.000 0.182 0.000 0.067DPE 0.000 0.157 0.076 0.000 0.000 0.000 0.068 0.000 0.000AE-TAEA 1.152 1.307 1.509 0.447 0.967 0.273 1.060 0.599 0.6511-TEPA 2.758 3.629 3.880 0.863 1.812 0.388 3.088 0.995 1.169AE-DAEP 0.000 0.343 0.336 0.000 0.000 0.000 0.222 0.000 0.000AE-PEEDA 0.000 0.145 0.157 0.000 0.000 0.000 0.112 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.334 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.099 0.291 0.000 0.000 0.000 0.106 0.000 0.000Others 1.043 2.132 3.402 0.377 0.694 0.316 1.555 0.738 0.659MEA Conversion, % 46.54 56.52 62.58 32.37 37.89 22.83 52.40 32.99 33.57DETA Conversion, % 12.92 20.49 20.25 6.35 10.36 5.33 15.81 7.99 8.76Acyclic (N4), % 97.22 89.18 91.48 99.05 97.62 100.00 96.06 98.82 97.97Acrylic (N5), % 100.00 89.36 82.82 100.00 100.00 100.00 90.40 100.00 100.00.SIGMA. (N5)/.SIGMA.(N4), 0.33 0.42 0.49 0.17 0.29 0.11 0.36 0.20 0.22weight ratioAcrylic (N4)/cyclic 5.31 2.33 3.05 9.26 6.48 11.31 4.55 6.94 6.80(< = N4), weight ratio__________________________________________________________________________ TABLE XXX__________________________________________________________________________Example No. 277 278 279 280 281 282 283 284 285Catalyst Type LL LL LL LL LL LL LL LL LL__________________________________________________________________________Catalyst weight, gm 70.6 70.6 70.6 70.6 70.6 70.6 70.6 70.6 70.6Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 267.9 267.8 277.8 259.9 270.1 259.9 280.1 269.6 269Time on organics, hrs. 5.0 7.5 26.0 31.5 50.0 55.5 74.0 78.0 80.0Duration of run, hrs. 1 1 2 2 2 2 2 2 1.5MEA SV, gmol/hr/kgcat 0.39 8.50 4.10 4.26 3.89 4.41 4.10 4.07 4.13DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 2.167 2.266 4.396 1.162 2.491 1.273 4.640 2.530 2.433MEA 28.978 28.688 26.446 33.928 28.222 33.924 23.574 29.868 29.121PIP 0.494 0.372 0.461 0.092 0.207 0.083 0.544 0.212 0.203DETA 48.084 52.021 51.406 57.383 55.479 56.855 50.221 53.418 55.210AEEA 1.425 1.525 1.038 1.006 1.321 1.043 1.027 1.313 1.296AEP 0.568 0.441 0.564 0.230 0.352 0.215 0.561 0.299 0.305HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.506 0.561 0.265 0.113 0.219 0.139 0.375 0.264 0.2661-TETA 7.871 6.131 3.828 1.714 4.080 1.741 5.218 3.019 3.221DAEP 0.101 0.000 0.095 0.124 0.000 0.000 0.085 0.000 0.000PEEDA 0.100 0.080 0.203 0.117 0.000 0.093 0.111 0.114 0.072DPE 0.117 0.000 0.254 0.107 0.132 0.000 0.309 0.118 0.097AE-TAEA 0.530 0.252 0.150 0.000 0.133 0.000 0.191 0.000 0.0001-TEPA 1.837 0.607 0.160 0.000 0.131 0.000 0.719 0.000 0.000AE-DAEP 0.100 0.000 0.000 0.000 0.000 0.000 0.112 0.000 0.000AE-PEEDA 0.000 0.157 0.147 0.000 0.000 0.000 0.178 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.101 0.093BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 2.103 1.740 5.237 1.773 2.532 1.674 5.777 2.917 2.755MEA Conversion, % 19.77 20.18 26.43 7.46 21.73 6.67 34.14 15.86 18.88DETA Conversion, % 20.89 13.97 15.01 6.98 8.55 7.04 16.62 10.56 8.60Acyclic (N4), % 96.35 98.82 88.13 84.00 97.03 95.30 91.72 93.42 95.39Acrylic (N5), % 95.93 84.54 67.84 0.00 100.00 0.00 75.87 0.00 0.00.SIGMA. (N5)/.SIGMA.(N4), 0.28 0.15 0.10 0.00 0.06 0.00 0.20 0.03 0.03weight ratioAcrylic (N4)/cyclic 6.07 7.50 2.60 2.72 6.22 4.81 3.47 4.42 5.16(< = N4), weight ratio__________________________________________________________________________ TABLE XXXI__________________________________________________________________________Example No. 286 287 288 289 290 291 292 293 294Catalyst Type MM MM MM MM MM MM MM MM MM__________________________________________________________________________Catalyst weight, gm 80.1 80.1 80.1 80.1 80.1 80.1 80.1 80.1 80.1Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.1 270 280.2 259.7 270.1 259.6 280 270 270Time on organics, hrs. 5.0 7.5 26.5 31.5 49.7 54.0 74.0 77.5 80.0Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.81 3.85 3.23 4.01 3.93 4.12 3.71 3.87 3.79DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude prodict composition, wt. %EDA 1.935 2.148 4.938 0.907 1.895 0.879 4.006 2.166 1.951MEA 18.750 21.318 20.112 30.534 28.213 31.731 24.388 29.089 28.221PIP 0.553 0.373 0.726 0.053 0.150 0.043 0.410 0.190 0.179DETA 50.396 52.368 51.336 60.802 57.134 60.506 53.455 57.017 58.930AEEA 0.561 0.915 0.707 0.796 1.023 0.782 0.908 1.152 1.167AEP 0.744 0.572 0.748 0.309 0.383 0.307 0.625 0.384 0.410HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.214 1.199 0.429 0.429 0.192 0.365 0.366 0.265 0.2661-TETA 9.307 8.213 5.708 1.341 2.862 1.182 4.049 2.751 2.937DAEP 0.134 0.098 0.388 0.083 0.164 0.000 0.099 0.107 0.177PEEDA 0.113 0.091 0.487 0.000 0.168 0.097 0.310 0.113 0.134DPE 0.111 0.074 0.489 0.000 0.145 0.000 0.313 0.141 0.126AE-TAEA 0.592 0.135 0.282 0.140 0.151 0.000 0.279 0.118 0.1521-TEPA 2.145 1.256 0.907 0.000 0.137 0.000 0.116 0.111 0.000AE-DAEP 0.105 0.097 0.165 0.000 0.000 0.000 0.000 0.000 0.000AE-PEEDA 0.221 0.227 0.312 0.000 0.000 0.000 0.129 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.085 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 7.869 5.765 6.160 1.656 2.354 1.509 5.848 2.786 2.669MEA Conversion, % 49.20 41.78 44.57 16.55 21.53 13.41 32.99 20.19 23.49DETA Conversion, % 18.85 15.01 15.92 1.24 5.56 1.86 12.71 7.03 5.05Acyclic (N4), % 96.71 97.29 81.81 95.55 86.50 94.12 85.94 89.31 88.02Acrylic (N5), % 89.37 81.10 67.94 100.00 100.00 0.00 75.42 100.00 100.00.SIGMA.(N5)/.SIGMA. (N4), 0.28 0.18 0.23 0.08 0.08 0.00 0.10 0.07 0.04weight ratioAcrylic (N4)/cyclic 6.36 7.80 2.16 3.98 3.03 3.47 2.51 3.23 3.12(< = N4), weight ratio__________________________________________________________________________ TABLE XXXII__________________________________________________________________________Example No. 295 296 297 298 299 300 301 302 303__________________________________________________________________________Catalyst Type NN NN NN NN NN NN NN NN NNCatalyst weight, gm 81.2 81.2 81.2 81.2 81.2 81.2 81.2 81.2 81.2Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.9 272.7 279.9 260.3 268.3 261.4 278.9 270.6 271.7Time on organics, hrs. 7.5 26.0 31.0 47.0 53.0 58.5 73.0 78.0 80.0Duration of run, hrs. 2 2 2 2 2 2.5 2 2 2MEA SV, gmol/hr/kgcat 3.80 3.43 3.59 3.68 3.75 4.01 3.56 3.87 3.87DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 1.775 2.809 2.208 1.431 2.058 0.987 4.151 1.948 1.942MEA 28.020 25.978 11.404 32.207 28.431 31.510 25.905 30.029 29.693PIP 0.108 0.150 0.000 0.069 0.120 0.040 0.254 0.118 0.112DETA 59.798 58.058 46.899 58.424 57.923 59.289 52.433 57.883 58.062AEEA 0.541 0.675 1.138 0.696 0.890 0.677 0.840 0.882 0.858AEP 0.313 0.348 1.766 0.248 0.320 0.252 0.449 0.311 0.322HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.092 0.169 1.615 0.393 0.129 0.398 0.234 0.129 0.1281-TETA 3.144 3.193 10.766 1.341 2.981 1.076 3.031 2.141 2.296DAEP 0.168 0.096 0.685 0.064 0.076 0.099 0.109 0.146 0.166PEEDA 0.243 0.153 0.635 0.058 0.167 0.147 0.177 0.113 0.141DPE 0.184 0.207 0.122 0.098 0.172 0.095 0.253 0.136 0.160AE-TAEA 0.203 0.120 2.095 0.000 0.159 0.000 0.298 0.115 0.1421-TEPA 0.216 0.000 5.688 0.179 0.000 0.121 0.099 0.000 0.000AE-DAEP 0.000 0.000 0.571 0.000 0.000 0.000 0.000 0.000 0.000AE-PEEDA 0.000 0.000 0.651 0.000 0.000 0.000 0.098 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.469 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.000 0.532 0.000 0.000 0.000 0.000 0.000 0.000Others 2.095 3.752 4.778 2.591 3.333 2.170 6.088 2.749 2.847MEA Conversion, % 23.74 28.57 68.94 12.45 22.42 13.61 27.80 17.72 18.86DETA Conversion, % 3.28 5.12 24.09 5.62 6.07 3.39 13.14 5.74 5.71Acyclic(N4), % 84.47 88.05 89.57 88.73 88.23 81.18 85.84 85.16 83.84Acyclic(N5), % 100.00 100.00 77.78 100.00 100.00 100.00 80.24 100.00 100.00.SIGMA.(N5)/.SIGMA.(N4), 0.11 0.03 0.72 0.09 0.05 0.07 0.13 0.04 0.05weight ratioAcyclic(N4)/cyclic 3.19 3.52 3.86 3.23 3.64 2.33 2.63 2.75 2.69(< = N4),weight ratio__________________________________________________________________________ TABLE XXXIII__________________________________________________________________________Example No. 304 305 306 307 308 309 310 311 312__________________________________________________________________________Catalyst Type OO OO OO OO OO OO OO OO OOCatalyst weight, gm 76.3 76.3 76.3 76.3 76.3 76.3 76.3 76.3 76.3Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.9 272.7 279.9 260.3 268.3 261.4 278.9 270.6 271.7Time on organics, hrs. 7.5 26.0 31.0 47.0 53.0 58.5 73.0 78.0 80.0Duration of run, hrs. 2 2 2 2 2 2.5 2 2 2MEA SV, gmol/hr/kgcat 3.99 3.68 4.09 2.65 1.23 0.96 3.38 3.80 3.31DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 1.574 1.791 4.858 0.968 2.024 2.100 2.080 0.921 0.937MEA 18.061 16.725 23.777 24.322 13.187 16.037 16.072 23.937 22.805PIP 1.056 0.060 0.323 0.500 1.357 1.136 1.291 0.528 0.587DETA 52.716 51.336 50.891 55.597 51.804 51.667 51.643 57.189 56.650AEEA 1.515 1.794 0.774 3.457 3.008 2.269 1.717 2.377 3.256AEP 1.413 1.302 0.469 0.517 1.435 1.300 1.360 0.518 0.660HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.676 1.719 0.290 0.781 1.672 1.529 1.523 0.820 0.8791-TETA 11.477 11.388 3.548 6.608 11.810 11.030 10.185 6.667 7.190DAEP 0.280 0.282 0.141 0.080 0.263 0.294 0.263 0.097 0.107PEEDA 0.193 0.215 0.257 0.000 0.192 0.203 0.206 0.000 0.067DPE 0.000 0.000 0.366 0.000 0.000 0.072 0.000 0.000 0.000AE-TAEA 0.773 0.861 0.327 0.406 0.810 0.775 0.789 0.456 0.5131-TEPA 3.017 3.327 0.123 0.963 3.541 3.449 2.992 1.036 1.135AE-DAEP 0.088 0.115 0.110 0.000 0.227 0.177 0.222 0.000 0.000AE-PEEDA 0.000 0.000 0.176 0.000 0.115 0.135 0.110 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.094 0.000 0.000 0.072 0.098 0.058 0.000 0.000Others 0.509 0.841 7.550 0.461 1.103 0.677 1.461 0.555 0.534MEA Conversion, % 50.94 53.95 33.72 32.83 63.87 55.94 55.35 34.29 37.73DETA Conversion, % 14.90 15.99 15.70 8.75 15.64 15.63 14.74 6.69 8.06Acyclic(N4), % 96.53 96.35 83.41 98.93 96.73 95.66 96.15 98.72 97.88Acyclic(N5), % 97.72 95.24 61.11 100.00 91.31 91.12 90.64 100.00 100.00.SIGMA.(N5)/.SIGMA.(N4), 0.28 0.32 0.16 0.18 0.34 0.35 0.34 0.20 0.20weight ratioAcyclic(N4)/cyclic 4.47 4.59 2.47 6.74 4.15 4.18 3.75 6.55 5.67(< = N4),weight ratio__________________________________________________________________________ TABLE XXXIV__________________________________________________________________________Example No. 313 314 315 316 317 318 319 320 321__________________________________________________________________________Catalyst Type PP PP PP PP PP PP PP PP PPCatalyst weight, gm 76.1 76.1 76.1 76.1 76.1 76.1 76.1 76.1 76.1Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270 270 280 260 270 260 280 270 269.4Time on organics, hrs. 5.5 24.0 29.5 48.5 53.5 72.0 77.5 93.0 94.0Duration of run, hrs. 2 2 2 2 2 2 2 1 1MEA SV, gmol/hr/kgcat 4.03 3.42 4.57 5.42 4.80 4.26 4.14 4.21 1.91DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 2.718 0.000 3.456 1.014 1.450 0.805 3.050 1.886 1.860MEA 13.198 13.705 10.445 24.724 21.688 32.394 18.370 26.238 25.429PIP 1.176 1.217 1.276 0.318 0.501 0.279 1.161 0.667 0.651DETA 44.099 47.849 45.082 54.434 53.648 46.319 42.468 43.338 42.572AEEA 1.298 1.149 0.783 1.841 1.512 2.946 1.159 2.722 2.762AEP 1.774 1.847 1.906 0.410 0.649 0.391 1.624 0.861 0.848HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.744 1.923 1.704 1.507 1.720 1.323 1.037 1.629 1.6561-TETA 12.612 12.764 11.841 8.466 10.127 7.262 9.928 9.641 10.039DAEP 0.762 0.661 0.856 0.081 0.169 0.072 0.671 0.224 0.201PEEDA 0.511 0.477 0.625 0.000 0.110 0.000 0.510 0.153 0.129DPE 0.135 0.166 0.089 0.000 0.000 0.000 0.101 0.076 0.000AE-TAEA 2.518 1.883 2.119 0.797 1.392 0.705 1.873 1.397 1.5071-TEPA 6.017 4.679 5.227 1.495 2.798 1.149 4.035 2.862 3.120AE-DAEP 0.397 0.354 0.577 0.000 0.000 0.000 0.486 0.102 0.214AE-PEEDA 0.098 0.000 0.207 0.000 0.000 0.000 0.102 0.000 0.103iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.180 0.219 0.363 0.000 0.000 0.000 0.246 0.303 0.151BPEA 0.182 0.198 0.325 0.000 0.000 0.000 0.200 0.174 0.113Others 1.581 2.529 4.320 0.513 0.856 0.383 4.070 1.426 1.246MEA Conversion, % 63.48 62.41 71.33 32.51 41.96 8.72 48.56 27.14 28.62DETA Conversion, % 27.47 22.01 26.47 11.69 14.67 22.43 29.33 28.48 28.98Acyclic(N4), % 91.07 91.84 89.61 99.19 97.70 99.17 89.54 96.14 97.25Acyclic(N5), % 90.88 89.49 83.31 100.00 100.00 100.00 85.10 88.03 88.85.SIGMA.(N5)/.SIGMA.(N4), 0.60 0.46 0.58 0.23 0.35 0.21 0.57 0.41 0.43weight ratioAcyclic(N4)/cyclic 3.29 3.36 2.85 12.33 8.29 11.56 2.70 5.69 6.40(< = N4),weight ratio__________________________________________________________________________ TABLE XXXV__________________________________________________________________________Example No. 322 323 324 325 326 327 328 329 330__________________________________________________________________________Catalyst Type QQ QQ QQ QQ QQ QQ QQ QQ QQCatalyst weight, gm 78.5 78.5 78.5 78.5 78.5 78.5 78.5 78.5 78.5Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.3 270.8 280.9 259.5 270.8 261.4 282.6 273.4 270.8Time on organics, hrs. 4.0 7.0 26.0 31.0 50.0 55.0 74.0 79.0 99.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.42 3.32 3.47 3.50 3.64 3.76 3.58 3.51 3.64DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 2.064 1.889 2.436 0.860 0.798 0.344 1.077 0.453 0.663MEA 14.084 15.810 12.462 36.060 25.744 30.392 15.607 22.241 25.522PIP 1.454 1.307 1.613 0.473 0.583 0.199 0.827 0.380 0.467DETA 51.792 51.235 52.756 54.948 56.753 59.500 53.106 59.354 60.415AEEA 0.857 1.123 0.758 1.393 0.172 1.675 1.251 1.785 0.264AEP 2.286 1.884 2.151 0.372 0.645 0.390 1.366 0.626 0.647HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.116 0.989 1.006 0.279 0.629 0.401 1.612 0.804 0.6291-TETA 12.082 10.881 10.297 2.687 6.508 4.381 11.880 6.933 5.481DAEP 0.742 0.738 0.685 0.000 0.135 0.000 0.271 0.099 0.151PEEDA 0.468 0.513 0.507 0.000 0.071 0.000 0.256 0.087 0.127DPE 0.000 0.133 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 1.823 1.579 1.601 0.000 0.441 0.000 0.202 0.000 0.3801-TEPA 5.194 4.155 4.031 0.000 0.624 0.000 3.427 0.617 0.349AE-DAEP 0.472 0.373 0.373 0.000 0.000 0.000 0.230 0.000 0.000AE-PEEDA 0.179 0.155 0.159 0.000 0.000 0.000 0.000 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.109 0.154 0.117 0.000 0.000 0.000 0.186 0.000 0.000BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 0.428 0.801 1.358 0.429 2.397 0.417 2.141 1.419 2.054MEA Conversion, % 62.62 57.18 65.91 1.08 29.53 17.71 57.46 38.96 31.32DETA Conversion, % 18.31 17.53 14.23 10.42 7.67 4.25 13.98 3.19 3.37Acyclic(N4), % 91.61 89.56 90.46 100.00 97.20 100.00 96.24 97.65 95.65Acyclic(N5), % 90.22 89.36 89.68 0.00 100.00 0.00 89.72 100.00 100.00.SIGMA.(N5)/.SIGMA.(N4), 0.54 0.48 0.50 0.00 0.14 0.00 0.29 0.08 0.11weight ratioAcyclic(N4)/cyclic 2.67 2.59 2.28 3.51 4.98 8.11 4.96 6.49 4.39(< = N4),weight ratio__________________________________________________________________________ TABLE XXXVI__________________________________________________________________________Example No. 331 332 333 334 335 336 337 338 339__________________________________________________________________________Catalyst Type RR RR RR RR RR RR RR RR RRCatalyst weight, gm 74.5 74.5 74.5 74.5 74.5 74.5 74.5 74.5 74.5Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 267.3 271.6 280.4 260.3 269.1 261.9 278.4 268.9 268.5Time on organics, hrs. 6.5 25.5 30.5 49.5 54.5 73.5 78.5 97.0 99.2Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.48 4.16 4.21 3.93 3.96 3.98 4.08 3.40 3.96DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 1.181 1.202 2.220 0.541 0.922 0.455 1.851 1.236 0.863MEA 24.149 27.125 24.297 32.485 29.621 31.003 24.872 30.577 28.781PIP 0.405 0.291 0.859 0.101 0.203 0.079 0.464 0.261 0.228DETA 57.182 59.913 55.802 60.897 60.714 62.348 54.893 58.708 61.316AEEA 0.929 1.479 1.151 1.074 1.180 0.920 1.384 1.342 1.371AEP 0.649 0.503 0.740 0.341 0.427 0.349 0.703 0.474 0.446HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.720 0.473 0.644 0.321 0.303 0.320 0.553 0.276 0.2911-TETA 7.014 4.341 6.500 1.844 3.136 1.875 6.108 2.942 3.059DAEP 0.113 0.000 0.109 0.000 0.098 0.000 0.348 0.090 0.090PEEDA 0.098 0.000 0.111 0.000 0.000 0.000 0.583 0.000 0.000DPE 0.000 0.000 0.083 0.000 0.000 0.000 0.182 0.000 0.000AE-TAEA 0.438 0.224 0.288 0.000 0.000 0.000 0.826 0.000 0.0001-TEPA 1.158 0.139 0.695 0.000 0.000 0.000 1.081 0.000 0.000AE-DAEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-PEEDA 0.105 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 1.839 1.060 2.010 0.836 1.046 0.930 2.604 0.915 0.887MEA Conversion, % 34.39 26.20 33.56 12.26 19.77 16.34 32.77 16.26 21.89DETA Conversion, % 7.68 3.12 9.31 2.25 2.27 0.01 11.81 4.45 1.10Acyclic(N4), % 97.35 100.00 95.92 100.00 97.24 100.00 85.69 97.27 97.40Acyclic(N5), % 93.82 100.00 100.00 0.00 0.00 0.00 100.00 0.00 0.00.SIGMA.(N5)/.SIGMA.(N4), 0.21 0.08 0.13 0.00 0.00 0.00 0.25 0.00 0.00weight ratioAcyclic(N4)/cyclic 6.12 6.06 3.75 4.89 4.73 5.13 2.92 3.90 4.39(< .times. N4),weight ratio__________________________________________________________________________ TABLE XXXVII__________________________________________________________________________Example No. 340 341 342 343 344 345 346 347 348__________________________________________________________________________Catalyst Type SS SS SS SS SS SS SS SS SSCatalyst weight, gm 84 84 84 84 84 84 84 84 84Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270 270 280 260 270 260 280 270 270Time on organics, hrs. 6.5 24.0 29.5 48.0 53.7 71.0 74.0 98.0 99.0Duration of run, hrs. 2 2 2 2 2 2 1 2 1MEA SV, gmol/hr/kgcat 2.92 2.94 2.91 3.00 3.21 2.85 3.69 3.28 3.38DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 3.143 3.522 6.151 1.751 3.148 1.874 5.153 2.734 2.608MEA 30.100 29.982 26.771 32.968 30.586 32.904 26.314 31.293 31.488PIP 0.084 0.091 0.154 0.000 0.064 0.042 0.115 0.055 0.064DETA 55.305 54.533 48.236 58.522 54.943 55.103 47.403 53.775 53.754AEEA 0.153 0.233 0.160 0.091 0.000 0.090 0.176 0.171 0.152AEP 0.295 0.276 0.352 0.223 0.245 0.200 0.308 0.227 0.225HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.380 0.387 0.555 0.226 1.227 0.630 0.434 0.277 0.2901-TETA 1.422 1.462 1.967 0.594 0.634 0.365 1.619 0.287 0.240DAEP 0.097 0.089 0.101 0.117 0.081 0.068 0.090 0.088 0.095PEEDA 0.084 0.081 0.215 0.150 0.109 0.121 0.166 0.158 0.167DPE 0.181 0.185 0.356 0.110 0.150 0.062 0.241 0.134 0.129AE-TAEA 0.000 0.000 0.184 0.000 0.000 0.000 0.122 0.000 0.0001-TEPA 0.133 0.000 0.123 0.000 0.148 0.103 0.000 0.000 0.000AE-DAEP 0.000 0.000 0.000 0.000 0.312 0.000 0.000 0.000 0.000AE-PEEDA 0.000 0.000 0.104 0.000 0.000 0.000 0.000 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 4.933 5.408 9.890 3.207 4.813 2.118 8.097 5.003 4.889MEA Conversion, % 17.10 17.35 25.92 10.37 15.66 6.14 22.88 11.56 10.89DETA Conversion, % 9.47 10.66 20.67 5.44 9.96 6.58 17.43 9.67 9.59Acyclic(N4), % 83.24 83.89 78.95 68.51 84.54 79.89 80.51 59.78 57.54Acyclic(N5), % 100.00 0.00 74.66 0.00 52.87 100.00 100.00 0.00 0.00.SIGMA.(N5)/.SIGMA.(N4), 0.06 0.00 0.13 0.00 0.13 0.08 0.05 0.00 0.00weight ratioAcyclic(N4)/cyclic 2.43 2.56 2.14 1.37 2.87 2.02 2.23 0.85 0.78(< .times. N4),weight ratio__________________________________________________________________________ TABLE XXXVIII__________________________________________________________________________Example No. 349 350 351 352 353 354 355 356 357__________________________________________________________________________Catalyst Type TT TT TT TT TT TT TT TT TTCatalyst weight, gm 80.7 80.7 80.7 80.7 80.7 80.7 80.7 80.7 80.7Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.6 269.6 279.5 260.0 269.8 259.2 280.0 271.4 269.4Time on organics, hrs. 20.5 24.5 44.0 49.0 68.0 73.0 92.0 97.0 116.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.55 3.63 3.60 3.78 3.52 3.53 3.01 3.34 3.20DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 1.354 1.094 2.246 0.684 1.032 0.457 2.918 1.351 1.546MEA 18.152 18.204 13.314 28.101 23.557 28.629 14.287 21.618 21.329PIP 0.850 0.723 1.703 0.353 0.902 0.303 2.036 0.844 1.106DETA 49.396 53.187 48.982 57.642 58.104 58.959 49.804 54.426 52.827AEEA 1.115 1.255 0.534 1.459 0.788 1.073 0.483 0.249 0.256AEP 1.250 0.946 2.103 0.528 0.967 0.526 2.138 1.089 1.122HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.869 1.413 1.083 0.729 0.404 0.462 0.770 1.319 1.2581-TETA 12.723 11.602 11.826 6.274 7.800 5.369 10.228 9.582 9.770DAEP 0.209 0.196 0.731 0.061 0.485 0.286 0.654 0.151 0.165PEEDA 0.152 0.141 0.630 0.000 0.281 0.137 0.454 0.114 0.115DPE 0.000 0.000 0.064 0.000 0.000 0.000 0.062 0.000 0.000AE-TAEA 0.956 1.039 2.383 0.000 0.000 0.000 1.590 0.000 0.0001-TEPA 3.937 3.244 5.190 0.326 0.168 0.000 3.399 0.708 0.786AE-DAEP 0.509 0.284 0.454 0.000 0.000 0.000 0.085 0.000 0.000AE-PEEDA 0.534 0.100 0.131 0.000 0.000 0.000 0.201 0.087 0.108iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 1.412 0.293 0.271 0.000 0.000 0.000 0.168 0.099 0.371BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 1.363 1.228 2.694 1.129 0.741 0.607 2.400 3.254 3.290MEA Conversion, % 51.28 50.92 64.50 24.02 35.62 22.13 60.51 41.07 41.44DETA Conversion, % 21.21 14.77 22.37 7.37 5.63 4.69 18.19 11.82 13.80Acyclic(N4), % 97.41 97.47 90.05 99.13 91.45 93.23 90.38 97.63 97.53Acyclic(N5), % 66.59 86.35 89.84 100.00 100.00 0.00 91.65 79.22 62.13.SIGMA.(N5)/.SIGMA.(N4), 0.53 0.37 0.59 0.05 0.02 0.00 0.45 0.08 0.11weight ratioAcyclic(N4)/cyclic 5.52 6.49 2.47 7.44 3.11 4.66 2.06 4.96 4.40weight ratio__________________________________________________________________________ TABLE XXXIX__________________________________________________________________________Example No. 358 359 360 361 362 363 364 365 366__________________________________________________________________________Catalyst Type UU UU UU UU UU UU UU UU UUCatalyst weight, gm 89 89 89 89 89 89 89 89 89Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270 270 280 260 270 260 270 270 270Time on organics, hrs. 6.5 24.0 29.5 48.0 53.7 71.0 24.0 98.0 99.0Duration of run, hrs. 2 2 2 2 2 2 2 2 1MEA SV, gmol/hr/kgcat 2.91 2.74 2.97 2.84 3.12 2.66 2.76 2.88 3.02DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 0.718 0.645 1.457 0.333 0.542 0.310 1.234 0.585 0.539MEA 27.595 26.525 25.356 30.520 27.336 29.634 25.529 26.745 28.074PIP 1.107 1.105 2.119 0.588 1.024 0.549 1.947 0.000 0.917DETA 57.184 57.402 53.992 60.160 55.509 55.391 54.113 54.836 55.562AEEA 1.254 1.122 0.744 1.059 0.901 0.959 0.906 1.108 1.108AEP 0.828 0.865 1.760 0.408 0.730 0.375 1.646 0.736 0.672HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.643 0.674 0.525 0.429 0.414 0.344 0.605 0.489 0.5121-TETA 5.227 5.572 5.376 3.427 4.632 2.912 6.015 5.284 4.209DAEP 0.127 0.144 0.312 0.000 0.117 0.000 0.350 0.115 0.094PEEDA 0.140 0.173 0.363 0.000 0.128 0.000 0.428 0.126 0.099DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 0.366 0.492 0.490 0.169 0.040 0.124 0.669 0.166 0.2741-TEPA 1.413 1.833 1.908 0.515 1.633 0.351 2.473 1.458 1.032AE-DAEP 0.000 0.000 0.150 0.000 0.000 0.000 0.136 0.098 0.000AE-PEEDA 0.000 0.000 0.131 0.000 0.000 0.000 0.136 0.079 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.112 0.000 0.000Others 0.277 0.238 0.707 0.082 0.575 0.000 0.491 0.374 0.208MEA Conversion, % 25.36 28.39 30.94 17.40 23.34 13.63 31.57 23.79 20.82DETA Conversion, % 8.07 7.90 12.61 3.24 7.49 4.05 13.80 7.13 6.87Acyclic(N4), % 95.65 95.17 89.74 100.00 95.38 100.00 89.49 95.99 96.08Acyclic(N5), % 100.00 100.00 89.50 100.00 100.00 100.00 89.11 90.17 100.00.SIGMA.(N5)/.SIGMA.(N4), 0.29 0.35 0.41 0.18 0.32 0.15 0.48 0.30 0.27weight ratioAcyclic(N4)/cyclic 2.67 2.73 1.30 3.87 2.52 3.52 1.51 5.90 2.65(< .times. N4),weight ratio__________________________________________________________________________ TABLE XL__________________________________________________________________________Example No. 367 368 369 370 371 372 373 374__________________________________________________________________________Catalyst Type VV VV VV VV VV VV VV VVCatalyst weight, gm 89 89 89 89 89 89 89 89Pressure, psig 600 600 600 600 600 600 600 600Temperature, .degree.C. 270 280 260 270 260 260 270 270Time on organics, hrs. 6.5 29.5 48.0 53.7 71.0 74.0 98.0 99.0Duration of run, hrs. 2 2 2 2 2 1 2 1MEA SV, gmol/hr/kgcat 3.60 4.04 3.87 3.77 3.63 3.82 3.80 4.14DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 0.213 0.589 0.063 0.237 0.132 0.597 0.268 0.221MEA 28.924 28.276 32.679 29.051 31.767 26.401 29.867 31.406PIP 0.577 1.302 0.331 0.637 0.305 1.250 0.636 0.606DETA 60.693 59.604 61.967 55.284 57.693 54.502 57.225 57.491AEEA 1.337 0.873 0.904 0.882 0.873 1.072 1.112 1.076AEP 0.468 1.015 0.268 0.432 0.237 0.913 0.463 0.406HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.446 0.369 0.216 0.202 0.171 0.391 0.328 0.2871-TETA 3.783 3.779 1.991 2.687 1.723 4.061 2.922 2.612DAEP 0.000 0.182 0.000 0.064 0.000 0.133 0.000 0.000PEEDA 0.000 0.236 0.000 0.000 0.000 0.175 0.000 0.000DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 0.194 0.224 0.000 0.000 0.000 0.289 0.138 0.0001-TEPA 0.663 0.879 0.000 0.296 0.000 1.049 0.455 0.350AE-DAEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 0.102 0.321 0.081 0.079 0.000 0.307 0.187 0.194MEA Conversion, % 21.74 24.03 11.82 14.35 8.93 24.03 15.55 11.95DETA Conversion, % 2.40 4.83 0.62 3.13 1.70 6.80 3.84 4.21Acyclic(N4), % 100.00 90.85 100.00 97.82 100.00 93.54 100.00 100.00Acyclic(N5), % 100.00 100.00 0.00 100.00 0.00 100.00 100.00 100.00.SIGMA.(N5)/.SIGMA.(N4), 0.20 0.24 0.00 0.10 0.00 0.28 0.18 0.12weight ratioAcyclic(N4)/cyclic 4.04 1.52 3.69 2.55 3.50 1.80 2.96 2.86(< .times. N4),weight ratio__________________________________________________________________________ TABLE XLI__________________________________________________________________________Example No. 375 376 377 378 379 380 381 382 383__________________________________________________________________________Catalyst Type WW WW WW WW WW WW WW WW WWCatalyst weight, gm 109.3 109.3 109.3 109.3 109.3 109.3 109.3 109.3 109.3Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 272.8 272.4 281.4 261.6 271.6 261.2 281.1 271.8 271.8Time on organics, hrs. 4.5 25.5 30.5 49.5 54.5 73.5 78.5 96.5 98.0Duration of run, hrs. 2 2 2 2 2 2 2 1 1MEA SV, gmol/hr/kgcat 2.41 2.58 2.54 2.56 2.62 2.46 2.37 2.35 2.01DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 2.497 6.772 12.561 3.271 5.650 3.027 8.398 6.989 6.342MEA 11.926 3.136 0.306 9.052 3.533 8.556 0.344 2.253 2.052PIP 1.508 3.617 5.688 2.203 3.219 2.114 3.924 3.679 3.432DETA 43.663 34.939 27.007 40.944 37.212 42.204 28.868 34.736 33.388AEEA 0.175 0.056 0.056 0.424 0.046 0.430 0.068 0.054 0.052AEP 2.674 6.800 10.087 3.163 5.751 2.837 8.269 5.679 5.546HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 5.276 2.471 0.713 3.624 2.701 3.372 1.567 2.339 2.3871-TETA 13.602 13.192 7.877 15.395 13.650 14.959 10.350 13.399 13.817DAEP 0.031 3.410 4.966 0.050 2.804 1.167 5.005 2.753 2.852PEEDA 0.402 1.586 3.460 0.670 1.378 0.689 3.719 1.712 1.642DPE 0.164 0.126 0.173 0.124 0.130 0.189 0.296 0.208 0.214AE-TAEA 4.114 2.399 0.888 3.396 2.480 3.259 1.667 2.421 2.6841-TEPA 4.558 5.996 3.503 6.285 6.269 6.192 5.083 6.762 7.401AE-DAEP 0.056 1.150 2.203 0.395 0.981 0.321 2.619 1.146 1.196AE-PEEDA 0.000 0.368 0.656 0.172 0.301 0.143 0.777 0.355 0.371iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.202 0.000 0.000 0.000 0.230 0.000 0.049BPEA 0.019 0.170 0.043 0.198 0.142 0.105 0.056 0.133 0.249Others 2.325 4.721 8.340 3.395 3.331 1.197 7.221 4.133 4.304MEA Conversion, % 67.86 91.64 99.18 75.79 90.41 76.63 99.08 93.85 94.36DETA Conversion, % 30.07 44.67 56.74 34.91 39.97 31.48 53.83 43.61 45.49Acyclic(N4), % 96.93 75.36 49.97 95.75 79.13 89.96 56.92 77.11 77.49Acyclic(N5), % 99.14 83.26 58.59 92.68 86.00 94.33 64.70 84.90 84.39.SIGMA.(N5)/.SIGMA.(N4), 0.45 0.49 0.44 0.53 0.49 0.49 0.50 0.53 0.57weight ratioAcyclic(N4)/cyclic 3.95 1.01 0.35 3.06 1.23 2.62 0.56 1.12 1.18(< .times. N4),weight ratio__________________________________________________________________________ TABLE XLII__________________________________________________________________________Example No. 384 385 386 387 388 389 390 391 392__________________________________________________________________________Catalyst Type XX XX XX XX XX XX XX XX XXCatalyst weight, gm 117 117 117 117 117 117 117 117 117Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 269.3 269.2 279.4 258.8 269.2 259.4 279.2 268.9 269.6Time on organics, hrs. 23.5 27.5 47.0 52.0 71.0 76.0 95.0 100.0 120.0Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 2.58 2.36 2.57 2.67 2.50 2.45 1.13 0.81 1.98DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 3.709 3.837 8.600 2.804 3.721 0.488 9.601 7.741 3.411MEA 9.936 9.370 5.731 16.450 9.968 25.695 3.708 7.550 16.344PIP 2.708 2.524 4.204 1.433 2.717 0.842 4.962 3.887 2.182DETA 38.446 38.390 33.775 45.291 38.571 55.220 34.097 37.900 43.567AEEA 0.291 0.324 0.317 0.339 0.292 0.367 0.388 0.526 0.391AEP 4.686 4.502 7.284 1.974 4.702 0.717 8.582 5.708 2.836HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 3.835 4.377 2.941 4.188 3.848 1.310 2.846 3.803 3.7471-TETA 8.969 9.950 7.471 9.662 8.998 6.251 8.150 9.402 9.633DAEP 1.874 1.752 2.889 0.521 1.880 0.065 2.947 1.720 0.876PEEDA 0.861 0.698 1.317 0.180 0.864 0.000 1.373 0.837 0.409DPE 0.078 0.000 0.059 0.000 0.078 0.000 0.000 0.000 0.000AE-TAEA 0.228 0.307 0.306 0.270 0.229 0.199 0.000 0.000 0.0001-TEPA 4.090 4.452 0.103 3.018 4.103 0.000 2.329 3.192 2.764AE-DAEP 0.690 0.464 0.318 0.583 0.692 0.000 0.787 0.451 0.000AE-PEEDA 0.231 0.161 0.259 0.301 0.232 0.000 0.000 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.068 0.115 0.462 1.425 0.068 0.000 0.359 0.000 0.257BPEA 0.160 0.349 0.515 0.765 0.161 0.000 0.358 0.278 0.000Others 8.818 8.017 13.158 2.876 8.846 1.176 7.923 4.755 2.383MEA Conversion, % 72.57 74.10 84.35 54.81 72.57 27.13 89.78 78.65 53.20DETA Conversion, % 36.91 36.95 45.17 26.06 36.91 6.93 44.14 36.31 25.86Acyclic(N4), % 81.99 85.39 70.94 95.19 81.99 99.14 71.79 83.78 91.24Acyclic(N5), % 78.98 81.38 20.83 51.69 78.98 100.00 60.77 81.41 91.50.SIGMA.(N5)/.SIGMA.(N4), 0.35 0.35 0.13 0.44 0.35 0.03 0.25 0.25 0.21weight ratioAcyclic(N4)/cyclic 1.25 1.51 0.66 3.37 1.25 4.66 0.62 1.09 2.12(< .times. N4),weight ratio__________________________________________________________________________ TABLE XLIII__________________________________________________________________________Example No. 393 394 395 396 397 398 399 400 401__________________________________________________________________________Catalyst Type YY YY YY YY YY YY YY YY YYCatalyst weight, gm 109.7 109.7 109.7 109.7 109.7 109.7 109.7 109.7 109.7Pressure, psig 599 600 600 600 600 600 600 600 600Temperature, .degree.C. 272.8 272.4 281.4 261.6 271.6 261.2 281.1 271.8 271.8Time on organics, hrs. 4.5 25.5 30.5 49.5 54.5 73.5 78.5 96.5 98.0Duration of run, hrs. 2 2 2 2 2 2 2 1 1MEA SV, gmol/hr/kgcat 2.30 2.46 2.44 2.27 2.30 2.79 2.53 3.81 2.50DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 2.261 1.959 2.786 1.241 1.755 1.003 1.824 1.913 1.114MEA 11.820 15.791 11.138 22.601 18.976 22.986 18.586 22.750 22.718PIP 1.520 1.200 1.593 0.719 1.121 0.694 1.109 1.280 0.748DETA 45.153 45.959 41.322 50.852 47.133 52.385 47.720 47.166 49.655AEEA 0.011 0.410 0.153 0.999 0.569 0.740 0.269 0.266 0.465AEP 2.740 1.799 2.738 1.065 1.366 0.830 1.702 2.957 1.051HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 4.881 4.991 5.095 4.056 4.454 3.564 3.729 2.475 3.4041-TETA 14.240 13.568 13.497 10.800 11.889 10.434 10.309 7.038 9.572DAEP 0.016 0.382 1.089 0.163 0.254 0.130 0.690 1.198 0.295PEEDA 0.211 0.138 0.463 0.071 0.110 0.061 0.347 0.648 0.149DPE 0.149 0.000 0.194 0.034 0.000 0.066 0.208 0.175 0.058AE-TAEA 3.624 3.300 4.229 1.833 2.595 1.438 2.605 1.218 2.1631-TEPA 4.655 3.616 5.175 2.182 2.918 1.629 3.169 1.628 2.578AE-DAEP 0.025 0.000 0.194 0.047 0.000 0.000 0.138 0.331 0.250AE-PEEDA 0.000 0.000 0.091 0.000 0.000 0.000 0.071 0.087 0.071iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000BPEA 0.044 0.000 0.126 0.000 0.000 0.000 0.000 0.000 0.000Others 1.451 0.368 1.796 0.219 0.402 0.081 0.814 2.102 0.506MEA Conversion, % 68.07 57.17 69.70 39.78 48.09 38.05 49.16 37.30 38.16DETA Conversion, % 27.50 25.91 33.19 19.47 23.36 16.10 22.42 22.74 19.67Acyclic(N4), % 98.07 97.27 91.41 98.23 97.82 98.20 91.85 82.48 96.27Acyclic(N5), % 99.18 100.00 95.81 98.83 100.00 100.00 96.51 87.21 93.66.SIGMA.(N5)/.SIGMA.(N4), 0.43 0.36 0.48 0.27 0.33 0.22 0.39 0.28 0.38weight ratioAcyclic(N4)/cyclic 4.12 5.27 3.06 7.24 5.73 7.86 3.46 1.52 5.64(< = N4),weight ratio__________________________________________________________________________ TABLE XLIV______________________________________Example No. 402 403 404 405______________________________________Catalyst Type ZZ ZZ ZZ ZZCatalyst weight, gm 91.33 91.33 91.33 91.33Pressure, psig 597 597 596 596Temperature, .degree.C. 270 284 258 272Time on organics, hrs. 20.5 25.5 44.5 49.5Duration of run, hrs. 2 2 2 2MEA SV, gmol/hr/kgcat 2.39 2.58 2.52 2.54DETA/MEA mole ratio 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 4.834 8.303 4.455 3.149MEA 5.992 2.084 9.647 10.990PIP 2.283 3.699 1.702 1.505DETA 24.621 19.876 30.406 33.928AEEA 1.216 0.261 1.338 2.268AEP 3.659 6.379 2.728 2.013HEP 0.000 0.000 0.000 0.000TAEA 1.286 0.698 1.273 1.5951-TETA 12.156 7.714 10.112 12.504DAEP 2.494 4.084 1.904 1.055PEEDA 1.717 3.007 0.160 0.699DPE 0.254 0.161 0.302 0.234AE-TAEA 2.896 1.747 2.455 2.9141-TEPA 10.186 6.866 8.071 8.571AE-DAEP 1.858 3.439 1.934 0.777AE-PEEDA 0.718 0.938 0.748 0.439iAE-PEEDA 0.000 0.000 0.000 0.000AE-DPE 0.091 0.255 0.169 0.039BPEA 0.403 0.377 0.505 0.558Others 14.617 19.011 15.441 9.062MEA Conversion, % 84.09 94.41 74.56 70.46DETA Conversion, % 61.16 68.33 52.34 45.81Acyclic(N4), % 75.07 53.70 82.79 87.64Acyclic(N5), % 80.99 63.23 75.82 86.37.SIGMA.(N5)/.SIGMA.(N4), 0.90 0.87 1.01 0.83weight ratioAcyclic(N4)/cyclic 1.29 0.49 1.68 2.56(< = N4),weight ratio______________________________________ TABLE XLV__________________________________________________________________________Example No. 406 407 408 409 410 411__________________________________________________________________________Catalyst Type AAA AAA AAA AAA AAA AAACatalyst weight, gm 107 107 107 107 107 107Pressure, psig 600 600 600 600 600 600Temperature, .degree.C. 277 277 277 313 314 314Time on organics, hrs. 3.0 18.7 20.7 26.0 42.7 44.7Duration of run, hrs. 1 16 2 2 16 2MEA SV, gmol/hr/kgcat 2.26 2.24 2.27 2.10 2.08 2.11NH.sub.3 feedrate, gm/hr 59 59 56 59 59 59Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84EDA -- -- -- -- -- --Liquid product composition,wt. %EDA 1.69 1.53 1.11 5.98 5.97 6.14MeEDA 0.00 0.00 0.00 0.00 0.00 0.00MEA 10.19 7.13 8.50 1.44 1.75 1.70EtEDA 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.17 1.29 1.08 4.26 4.38 4.67DETA 63.75 67.41 69.62 56.36 56.78 56.34AEEA 1.16 0.51 0.78 0.78 0.78 0.78AEP 1.48 1.64 1.20 5.91 5.77 5.86HEP 0.00 0.00 0.00 0.07 0.09 0.07TETA's 13.90 13.58 11.94 14.21 13.22 13.20TEPA's 4.76 4.63 3.90 5.29 3.76 3.77ROH Conversion % 56.11 69.33 63.43 93.70 92.18 92.41Acyclic (N4)/cyclic 16.2 13.3 20.9 2.2 2.0 2.0(< = N4), weight ratioAcyclic (N5)/cyclic 11.6 10.9 16.1 1.2 2.2 2.4(< = N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- --weight ratio__________________________________________________________________________ TABLE XLVI__________________________________________________________________________Example No. 412 413 414 415 416 417 418 419 420 421__________________________________________________________________________Catalyst Type BBB BBB BBB BBB BBB BBB BBB BBB BBB BBBCatalyst weight, gm 123.7 123.7 123.7 123.7 123.7 123.7 123.7 123.7 123.7 123.7Pressure, psig 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 266 272 271 270 298 300 300 299 303 302Time on organics, hrs. 10.5 15.5 32.5 34.5 40.5 55.5 57.5 63.0 81.5 129.5Duration of run, hrs. 10 2 16 2 2 15 15 2 2 2MEA SV, gmol/hr/kgcat 1.94 1.72 1.97 1.97 2.02 1.94 0.26 1.88 1.97 1.89NH.sub.3 feedrate, gm/hr 38.4 56.0 57.0 63.0 59.0 60.2 57.5 57.0 58.5 46.5Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 77.16 77.16 77.16 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 22.84 22.84 22.84 22.84Liquid product composition,wt. %EDA 0.97 1.21 1.01 0.94 3.46 2.86 2.63 2.72 2.46 2.44MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 13.53 11.37 11.57 12.57 4.80 6.56 7.31 7.23 8.08 7.91EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.63 0.72 0.58 0.58 2.14 1.81 1.37 1.78 1.56 1.61DETA 74.34 73.54 74.39 75.32 69.81 71.72 73.83 72.52 73.94 73.16AEEA 0.91 0.72 0.86 0.86 0.34 0.32 0.28 0.39 0.52 0.47AEP 0.59 0.81 0.71 0.63 2.42 1.93 1.74 1.74 1.55 1.59HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 7.74 9.46 8.96 7.68 12.10 10.11 8.91 9.43 8.16 7.76TEPA's 1.07 1.81 1.48 1.17 2.94 2.34 1.88 2.12 1.79 1.93ROH Conversion % 41.89 51.36 50.41 46.08 79.45 71.67 68.42 68.80 65.08 65.40Acyclic (N4)/cyclic 100.0 73.1 38.5 74.8 8.1 8.9 10.6 9.9 10.1 9.4(< = N4), weight ratioAcyclic (N5)/cyclic -- -- -- -- -- 5.1 5.5 8.0 8.2 5.2(< = N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- -- -- -- --weight ratio__________________________________________________________________________ TABLE XLVII__________________________________________________________________________Example No. 422 423 424 425 426 427 428 429 430__________________________________________________________________________Catalyst Type CCC CCC CCC CCC CCC CCC CCC CCC CCCCatalyst weight, gm 105.7 105.7 105.7 105.7 105.7 105.7 105.7 105.7 105.7Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 268 281 275 302 304 304 303 302 302Time on organics, hrs. 4.7 19.7 21.7 26.7 43.7 45.7 51.2 66.7 68.7Duration of run, hrs. 2 15 2 2 17 2 2 14 2MEA SV, gmol/hr/kgcat 2.09 2.13 2.20 2.06 2.14 2.09 1.90 2.02 1.91NH.sub.3 feedrate, gm/hr 49.5 42.8 54.5 47.5 51.0 41.5 54.5 58.8 53.0Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- --AEEA -- -- -- -- -- -- 33.54 33.54 33.54Liquid product composition,wt. %EDA 2.25 1.42 1.17 4.33 4.33 4.06 2.41 2.32 2.62MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 8.59 11.37 12.86 5.60 6.05 5.73 0.00 0.00 0.00EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.36 0.68 0.49 1.69 1.70 1.69 9.19 9.15 9.13DETA 70.30 74.76 76.82 71.05 71.22 71.97 68.27 68.90 70.40AEEA 0.80 0.97 0.85 0.31 0.40 0.00 1.15 1.10 0.53AEP 1.27 0.69 0.53 1.68 1.67 1.61 1.32 1.33 1.51HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 10.97 8.09 5.52 9.47 8.65 7.79 6.49 6.41 6.60TEPA's 2.93 1.60 0.93 2.07 1.87 1.65 7.25 7.27 5.87ROH Conversion % 63.07 51.25 44.36 75.40 73.30 74.34 96.50 96.70 98.40Acyclic (N4)/cyclic 9.09 72.20 100.00 8.90 8.70 7.90 0.30 0.30 0.30(< = N4), weight ratioAcyclic (N5)/cyclic 28.90 100.00 100.00 15.10 10.60 9.60 13.10 13.60 9.50(< = N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 1.10 1.10 0.90weight ratio__________________________________________________________________________ TABLE XLVIII__________________________________________________________________________Example No. 431 432 433 434 435 436 437 438 439 440 441__________________________________________________________________________Catalyst Type DDD DDD DDD DDD DDD DDD DDD DDD DDD DDD DDDCatalyst weight, gm 121 121 121 121 121 121 121 121 121 121 121Pressure, psig 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 279 270 270 269 269 275 270 272 274 272 258Time on organics, hrs. 4.5 18.5 35.5 37.5 43.5 54.5 62.5 66.0 82.0 84.0 90.7Duration of run, hrs. 2 2 16 2 2 2 2 2 15 2 2MEA SV, gmol/hr/kgcat 2.00 1.98 1.98 2.03 2.03 2.01 1.97 1.68 1.70 1.69 1.33NH.sub.3 feedrate, gm/hr 67.2 72.0 48.1 46.0 44.5 41.1 47.5 48.0 45.1 49.0 86.5Liquid feed composition,wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- --AEEA -- -- -- -- -- -- -- 33.54 33.54 33.54 33.54Liquid product composition,wt. %EDA 5.79 1.61 1.48 1.43 1.18 1.34 1.37 1.05 1.04 1.08 0.48MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 2.74 6.67 7.72 7.67 7.39 6.27 6.43 0.31 0.11 0.12 0.15EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 4.65 1.25 1.17 1.16 0.99 1.15 1.21 10.37 10.57 10.55 7.06DETA 61.98 71.25 73.17 73.07 69.92 68.69 68.71 58.64 58.83 59.53 67.06AEEA 0.00 0.16 0.22 0.24 0.45 0.42 0.37 5.96 6.64 6.72 15.36AEP 5.74 1.29 0.94 0.93 0.97 1.13 1.18 1.35 1.26 1.20 0.59HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 13.80 14.03 12.81 12.89 14.92 16.23 15.76 8.51 8.04 7.49 3.04TEPA's 3.53 2.45 1.96 2.10 3.18 3.62 3.71 10.70 11.09 10.99 6.08ROH Conversion % 88.45 71.55 67.20 67.43 68.55 73.37 72.65 82.40 80.50 80.30 55.20Acyclic (N4)/cyclic 3.69 8.70 46.60 49.50 44.30 38.60 34.50 0.25 0.17 0.18 0.12(< = N4), weight ratioAcyclic (N5)/cyclic 2.70 100.00 100.00 100.00 100.00 100.00 100.00 34.00 38.70 44.00 100.00(< = N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- -- 1.30 1.40 1.50 2.00weight ratio__________________________________________________________________________ TABLE XLIX__________________________________________________________________________Example No. 442 443 444 445 446 447 448 449 450__________________________________________________________________________Catalyst Type EEE EEE EEE EEE EEE EEE EEE EEE EEECatalyst weight, gm 118.7 118.7 118.7 118.7 118.7 118.7 118.7 118.7 118.7Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 267 268 267 289 284 301 291 298 260Time on organics, hrs. 8.5 19.0 21.0 25.0 28.0 32.0 35.0 39.0 43.0Duration of run, hrs. 2 10 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 2.01 2.04 2.11 2.00 1.94 1.58 1.65 1.57 1.68NH.sub.3 feedrate, gm/hr 45.2 47.4 47.5 54.0 51.0 46.0 43.0 30.0 46.0Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 -- -- -- --AEEA -- -- -- -- -- 33.54 33.54 33.54 33.54Liquid product composition,wt. %EDA 1.12 0.95 0.83 2.89 2.86 2.46 1.69 2.41 0.31MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 11.83 12.17 12.64 6.50 6.93 0.45 0.52 0.34 0.45EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.94 0.63 0.49 1.87 1.84 11.04 10.33 11.22 3.39DETA 76.42 79.20 76.28 68.84 71.08 57.52 61.86 67.91 75.51AEEA 0.36 0.28 0.54 0.17 0.17 0.90 2.98 0.97 17.00AEP 0.63 0.39 0.41 1.88 1.71 2.52 1.37 1.71 0.27HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 7.47 5.50 7.52 11.98 10.95 11.25 8.74 6.93 1.01TEPA's 1.02 0.54 0.97 3.35 2.49 8.61 9.41 5.34 2.07ROH Conversion % 49.35 47.67 45.70 71.94 70.17 97.30 91.10 97.10 49.80Acyclic (N4)/cyclic 100.00 100.00 100.00 10.60 13.70 0.30 0.20 0.20 0.20(< = N4), weight ratioAcyclic (N5)/cyclic 100.00 100.00 100.00 5.78 8.20 4.40 22.80 100.00 100.00(< = N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- 0.80 1.10 0.80 2.00weight ratio__________________________________________________________________________ TABLE L__________________________________________________________________________Example No. 451 452 453 454 455 456 457 458 459 460 461 462__________________________________________________________________________Catalyst Type FFF FFF FFF FFF FFF FFF FFF FFF FFF FFF FFF FFFCatalyst weight, gm 123.6 123.6 123.6 123.6 123.6 123.6 123.6 123.6 123.6 123.6 123.6 123.6Pressure, psig 600 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 279 277 276 260 263 264 261 262 263 274 277 276Time on organics, hrs. 4.7 22.0 24.0 29.0 45.0 47.0 52.5 69.0 71.0 76.5 93.5 95.0Duration of run, hrs. 2 17 2 2 16 2 2 16 2 2 16 1MEA SV, gmol/hr/kgcat 1.92 1.96 1.93 1.96 1.97 1.99 1.73 1.70 1.74 1.65 1.66 1.73NH.sub.3 feedrate, gm/hr 53.0 48.4 55.0 52.0 49.3 49.5 47.0 47.3 46.5 49.0 49.9 54.6Liquid feed composition, wt. %PIP -- -- -- -- -- -- -- -- -- -- -- --DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- -- -- --AEEA -- -- -- -- -- -- 33.54 33.54 33.54 33.54 33.54 33.54Liquid product composition,wt. %EDA 3.96 3.55 3.17 1.21 1.14 1.30 0.77 0.77 0.67 1.58 1.88 1.60MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 2.91 2.56 2.50 7.40 7.44 7.38 0.18 0.00 0.00 0.00 0.00 0.00EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 3.12 2.46 2.21 1.06 1.05 1.15 8.23 8.70 8.57 10.86 10.76 10.60DETA 61.14 63.82 60.32 71.24 72.08 68.84 65.43 66.94 69.33 65.27 62.85 65.63AEEA 0.00 0.00 0.00 0.00 0.00 0.29 3.28 3.21 3.00 0.42 0.35 0.00AEP 4.38 3.42 3.06 1.06 0.99 1.07 0.00 0.91 0.88 1.66 1.77 1.70HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 17.74 18.49 18.86 15.11 14.78 15.71 6.46 5.73 5.20 7.71 8.60 7.54TEPA's 4.05 4.67 5.70 2.73 2.32 3.70 14.12 13.23 12.12 11.71 11.80 11.62ROH Conversion % 87.61 89.27 89.19 68.76 68.57 68.77 90.40 90.70 91.30 99.80 99.00 100.00Acyclic (N4)/cyclic 7.20 11.20 11.20 80.70 100.00 46.90 0.30 0.20 0.10 0.20 0.30 0.20(< = N4), weight ratioAcyclic (N5)/cyclic 100.00 18.00 17.30 100.00 100.00 100.00 85.10 94.20 100.00 35.10 26.40 30.80(< = N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 2.20 2.30 2.30 1.50 1.40 1.50weight ratio__________________________________________________________________________ TABLE LI__________________________________________________________________________Example No. 463 464 465 466 467 468 469 470 471 472 473__________________________________________________________________________Catalyst Type GGG GGG GGG GGG GGG GGG GGG GGG GGG GGG GGGCatalyst weight, gm 116.6 116.6 116.6 116.6 116.6 116.6 116.6 116.6 116.6 116.6 116.6Pressure, psig 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 277 284 272 272 277 266 267 266 282 282 281Time on organics, hrs. 4.5 20.0 22.0 27.5 44.5 52.5 69.5 71.5 76.5 94.5 96.5Duration of run, hrs. 2 15 2 2 15 2 2 2 2 16 2MEA SV, gmol/hr/kgcat 2.02 2.05 2.13 2.03 2.02 1.76 1.80 1.79 1.72 2.04 2.06NH.sub.3 feedrate, gm/hr 60.5 54.7 57.0 54.5 43.5 68.5 53.1 45.5 66.0 60.6 56.0Liquid feed composition,wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46 77.16 77.16MEA 22.84 22.84 22.84 22.84 22.84 -- -- -- -- 22.84 22.84AEEA -- -- -- -- -- 33.54 33.54 33.54 33.54 -- --Liquid product composition,wt. %EDA 2.05 2.24 1.23 0.78 0.73 0.38 0.32 0.39 1.58 2.16 2.07MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 5.90 3.75 6.68 8.22 8.34 0.26 0.00 0.19 0.00 4.77 4.91EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 2.21 2.48 1.56 1.14 1.10 6.66 6.97 6.77 9.99 2.49 2.37DETA 74.52 75.33 75.56 79.77 81.46 72.66 76.76 73.28 65.22 73.27 75.76AEEA 0.00 0.00 0.00 0.00 0.00 6.14 5.08 6.32 0.00 0.00 0.00AEP 2.09 2.54 1.56 1.05 1.06 0.64 0.61 0.59 1.90 2.48 2.38HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 11.24 11.94 11.23 8.09 6.69 5.09 4.22 4.81 9.47 10.79 10.14TEPA's 1.89 1.67 2.03 0.92 0.62 7.62 5.92 7.17 9.26 3.34 2.36ROH Conversion % 75.18 84.30 71.82 65.14 64.60 82.00 85.20 81.60 100.00 79.85 79.41Acyclic (N4)/cyclic 15.00 12.40 17.20 100.00 100.00 0.11 0.00 0.10 0.20 7.30 8.40(< = N4), weight ratioAcyclic (N5)/cyclic 100.00 100.00 100.00 100.00 100.00 62.00 100.00 70.20 7.21 2.50 7.40(< = N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- 1.30 1.40 1.50 1.00 -- --weight ratio__________________________________________________________________________ TABLE LII__________________________________________________________________________Example No. 474 475 476 477 478 479 480 481 482 483 484 485__________________________________________________________________________Catalyst Type HHH HHH HHH HHH HHH HHH HHH HHH HHH HHH HHH HHHCatalyst weight, gm 118.4 118.4 118.4 118.4 118.4 118.4 118.4 118.4 118.4 118.4 118.4 118.4Pressure, psig 600 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 267 276 276 295 296 296 298 270 271 266 267 268Time on organics, hrs. 8.0 21.0 23.0 29.0 45.0 47.0 53.0 69.0 71.0 77.0 93.0 95.0Duration of run, hrs. 2 13 2 2 16 2 2 16 2 2 16 2MEA SV, gmol/hr/kgcat 1.96 2.00 2.06 2.01 1.99 2.01 1.68 1.72 1.71 1.98 2.00 2.01NH.sub.3 feedrate, gm/hr 65.5 57.4 53.5 59.0 46.6 36.0 64.0 49.5 51.5 51.0 49.3 49.5Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 77.16 77.16 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- 22.84 22.84 22.84AEEA -- -- -- -- -- -- 33.54 33.54 33.54 -- -- --Liquid product composition,wt. %EDA 0.81 0.99 1.00 3.45 3.60 3.29 2.33 0.00 0.37 0.27 0.48 0.51MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 8.16 6.51 7.10 1.45 2.25 2.43 0.00 0.00 0.00 10.27 10.50 10.46EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.03 1.41 1.44 3.95 4.17 4.13 12.33 6.69 6.85 0.80 0.75 0.77DETA 77.87 78.14 74.65 76.12 72.14 74.46 69.31 82.62 77.14 84.56 84.28 84.63AEEA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4.62 6.65 0.00 0.00 0.00AEP 1.04 1.43 1.38 4.56 4.28 4.25 3.27 0.72 0.61 0.74 0.72 0.71HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 9.61 9.93 11.80 9.39 10.88 9.44 8.73 2.75 3.71 2.87 2.89 2.61TEPA's 1.49 1.59 2.63 1.08 2.34 1.86 3.29 2.60 4.50 0.49 0.39 0.00ROH Conversion % 65.45 72.55 70.09 93.97 90.62 89.88 100.00 86.50 80.60 56.14 55.12 55.13Acyclic (N4)/cyclic 53.30 37.90 23.80 4.10 4.40 4.10 0.20 0.00 0.00 100.00 100.00 100.00(< = N4), weight ratioAcyclic (N5)/cyclic 100.00 100.00 100.00 1.90 2.10 2.00 5.40 100.00 100.00 100.00 100.00 100.00(< = N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 0.40 1.00 1.20 -- -- --weight ratio__________________________________________________________________________ TABLE LIII__________________________________________________________________________Example No. 486 487 488 489 490 491 492 493 494 495 496 497__________________________________________________________________________Catalyst Type III III III III III III III III III III III IIICatalyst weight, gm 118.2 118.2 118.2 118.2 118.2 118.2 118.2 118.2 118.2 118.2 118.2 118.2Pressure, psig 600 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 272 271 273 299 301 300 302 302 273 270 272 272Time on organics, hrs. 4.0 17.0 19.0 25.0 42.5 44.5 50.5 59.0 62.0 72.7 82.0 84.0Duration of run, hrs. 2 13 2 2 17 2 2 8 2 2 9 2MEA SV, gmol/hr/kgcat 1.98 1.99 1.98 1.98 1.96 2.02 1.69 1.68 1.67 1.99 2.08 2.01NH.sub.3 feedrate, gm/hr 69.0 70.7 59.0 55.5 49.9 65.5 48.0 47.8 57.5 45.0 44.0 41.0Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 77.16 77.16 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- 22.84 22.84 22.84AEEA -- -- -- -- -- -- 33.54 33.54 33.54 -- -- --Liquid product composition,wt. %EDA 0.74 0.72 0.58 2.88 2.15 2.01 1.65 1.44 0.00 0.21 0.22 0.00MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 7.89 7.63 8.40 1.99 3.10 3.86 0.00 0.00 0.19 11.14 11.57 11.60EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.28 1.11 0.93 3.30 3.03 2.79 12.61 12.29 7.23 0.82 0.77 0.77DETA 79.77 73.47 73.54 76.57 79.28 79.79 71.48 70.87 78.08 84.83 84.22 85.08AEEA 0.23 0.50 0.70 0.00 0.00 0.00 0.00 0.00 7.36 0.00 0.00 0.00AEP 0.78 1.01 0.88 2.61 2.05 1.80 1.93 1.71 0.19 0.29 0.25 0.21HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 7.63 11.54 11.52 8.85 6.88 7.59 5.61 6.10 2.44 1.85 2.29 1.69TEPA's 1.03 2.90 2.71 1.72 1.36 1.22 3.11 4.22 3.46 0.37 0.26 0.19ROH Conversion % 66.33 67.44 64.22 91.52 86.72 83.64 100.00 100.00 78.20 52.05 50.20 50.04Acyclic (N4)/cyclic (< = 22.50 26.60 14.70 14.70 5.70 2.30 0.20 0.20 0.10 100.00 100.00 100.00N4), weight ratioAcyclic (N5)/cyclic (< = 100.00 33.50 100.00 100.00 4.50 1.90 1.90 2.90 14.00 100.00 100.00 100.00N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 0.60 0.70 1.40 -- -- --weight ratio__________________________________________________________________________ TABLE LIV__________________________________________________________________________Example No. 498 499 500 501 502 503 504 505 506 507 508 509__________________________________________________________________________Catalyst Type JJJ JJJ JJJ JJJ JJJ JJJ JJJ JJJ JJJ JJJ JJJ JJJCatalyst weight, gm 118.3 118.3 118.3 118.3 118.3 118.3 118.3 118.3 118.3 118.3 118.3 118.3Pressure, psig 600 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 272 271 272 300 302 302 301 274 275 275 276 276Time on organics, hrs. 4.0 17.5 19.5 25.0 41.0 43.0 48.0 65.0 67.0 72.0 85.0 87.0Duration of run, hrs. 2 13 2 2 16 2 2 16 2 2 15 2MEA SV, gmol/hr/kgcat 1.94 1.98 1.91 1.92 1.90 1.89 3.34 3.38 3.37 2.03 1.96 1.97NH.sub.3 feedrate, gm/hr 45.0 45.9 48.5 46.0 58.4 55.0 55.5 53.0 50.5 52.5 51.0 49.5Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 77.16 77.16 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- 22.84 22.84 22.84AEEA -- -- -- -- -- -- 33.54 33.54 33.54 -- -- --Liquid product composition,wt. %EDA 0.48 0.50 0.45 2.70 2.96 2.83 2.44 0.36 0.40 0.51 0.50 0.59MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 9.18 9.77 9.84 2.44 2.92 2.93 0.00 0.30 0.29 10.04 10.18 10.47EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.10 1.10 1.07 3.88 3.86 3.85 11.79 7.03 7.40 1.33 1.23 1.21DETA 77.40 77.67 78.15 68.03 67.03 66.76 61.93 69.26 69.84 76.33 78.33 77.59AEEA 0.64 0.63 0.64 0.00 0.07 0.08 0.00 7.10 6.01 0.69 0.48 0.51AEP 0.85 0.84 0.82 3.78 3.70 3.69 2.60 0.76 0.77 0.99 0.91 0.90HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00TETA's 7.04 6.84 6.47 11.12 10.94 11.03 9.81 5.55 5.66 7.02 6.22 6.15TEPA's 1.55 1.50 1.37 3.72 3.61 3.73 6.68 7.38 7.33 2.09 1.31 1.37ROH Conversion % 60.31 57.98 57.64 89.42 87.25 87.18 100.00 78.90 82.20 56.92 56.32 54.87Acyclic (N4)/cyclic (< = 22.40 22.90 21.20 4.00 4.10 4.00 0.30 0.10 0.10 13.50 21.40 20.40N4), weight ratioAcyclic (N5)/cyclic (< = 100.00 100.00 100.00 2.30 2.30 2.20 2.10 19.10 20.10 9.40 100.00 100.00N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 0.70 1.30 1.30 -- -- --weight ratio__________________________________________________________________________ TABLE LV__________________________________________________________________________Example No. 510 511 512 513 514 515 516 517 518__________________________________________________________________________Catalyst Type KKK KKK KKK KKK KKK KKK KKK KKK KKKCatalyst weight, gm 116.2 116.2 116.2 116.2 116.2 116.2 116.2 116.2 116.2Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 281 289 255 253 308 300 297 272 268Time on organics, hrs. 8.5 17.5 65.0 67.0 73.0 88.5 90.5 96.7 114.5Duration of run, hrs. 2 9 10 2 2 15 2 2 2MEA SV, gmol/hr/kgcat 1.95 1.92 1.68 1.73 1.62 1.74 1.71 1.68 1.72NH.sub.3 feedrate, gm/hr 47.2 45.6 46.8 45.0 44.0 43.3 47.0 43.0 46.5Liquid feed composition, wt. %DETA 77.16 77.16 66.46 66.46 77.16 77.16 77.16 66.46 66.46MEA 22.84 22.84 -- -- 22.84 22.84 22.84 -- --AEEA -- -- 33.54 33.54 -- -- -- 33.54 33.54Liquid product composition,wt. %EDA 2.23 1.99 0.37 0.35 9.13 5.71 5.98 1.22 1.22MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 9.36 10.47 0.39 0.36 4.75 8.86 8.41 0.45 0.45EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.65 0.44 1.26 1.29 1.40 0.90 0.92 3.43 3.43DETA 75.37 77.92 74.89 76.09 63.34 69.29 67.65 74.85 74.85AEEA 0.45 0.44 20.42 19.29 0.21 0.22 0.32 11.31 11.31AEP 0.71 0.52 0.00 0.00 1.52 1.00 1.05 0.45 0.45HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 6.89 4.55 0.22 0.21 6.49 5.50 6.02 2.05 2.05TEPA's 1.28 0.49 0.96 0.89 0.99 0.57 0.79 3.05 3.05ROH Conversion % 58.81 53.66 38.40 41.80 76.90 58.71 60.45 65.60 65.60Acyclic (N4)/cyclic (< = N4), 20.00 41.60 0.00 0.00 4.70 7.80 8.10 0.30 0.20weight ratioAcyclic (N5)/cyclic (< = N5), 100.00 100.00 100.00 100.00 2.50 100.00 100.00 100.00 100.00weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- 4.40 4.20 -- -- -- 1.50 1.50weight ratio__________________________________________________________________________ TABLE LVI__________________________________________________________________________Example No. 519 520 521 522 523 524 525 526 527 528 529__________________________________________________________________________Catalyst Type LLL LLL LLL LLL LLL LLL LLL LLL LLL LLL LLLCatalyst weight, gm 131.5 131.5 131.5 131.5 131.5 131.5 131.5 131.5 131.5 131.5 131.5Pressure, psig 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 273 277 277 305 300 300 300 303 301 278 276Time on organics, hrs. 5.0 21.7 23.7 29.0 45.0 47.0 53.0 70.0 72.0 76.0 80.0Duration of run, hrs. 2 15 2 1 16 2 2 16 2 2 2MEA SV, gmol/hr/kgcat 1.86 1.78 1.86 1.39 1.71 1.52 1.54 1.50 1.57 1.54 1.75NH.sub.3 feedrate, gm/hr 53.0 48.6 45.0 49.0 45.0 50.5 54.5 48.0 53.0 50.0 47.0Liquid feed composition,wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- -- 22.84AEEA -- -- -- -- -- -- 33.54 33.54 33.54 33.54 --Liquid product composition,wt. %EDA 0.39 0.41 0.44 4.14 1.93 1.70 1.17 1.32 1.32 0.35 0.48MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 12.44 11.40 11.03 1.91 5.20 5.43 0.00 0.00 0.00 0.00 10.23EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.04 1.00 0.97 4.80 2.81 2.65 9.73 9.94 10.69 7.37 1.48DETA 77.93 79.28 78.81 69.34 71.17 73.05 72.15 68.24 72.00 76.09 78.06AEEA 0.76 0.54 0.58 0.00 0.00 0.00 0.00 0.00 0.00 3.28 0.50AEP 0.86 0.88 0.85 5.19 2.82 2.57 2.10 2.26 2.37 0.74 1.14HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 5.36 5.49 5.87 10.35 10.83 10.10 7.69 8.66 7.72 5.03 5.65TEPA's 0.88 0.66 0.82 1.52 2.87 2.53 5.44 6.42 4.62 6.46 1.98ROH Conversion % 46.63 51.16 52.65 91.86 77.72 76.79 100.00 100.00 100.00 90.40 56.31Acyclic (N4)/cyclic (< = 20.20 25.50 22.70 3.20 6.60 7.30 0.20 0.20 0.20 0.10 5.90N4), weight ratioAcyclic (N5)/cyclic (< = 100.00 100.00 100.00 1.70 6.80 8.20 11.40 7.50 8.30 52.40 18.50N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 0.70 0.70 0.60 1.30 --weight ratio__________________________________________________________________________ TABLE LVII__________________________________________________________________________Example No. 530 531 532 533 534 535 536 537__________________________________________________________________________Catalyst Type MMM MMM MMM MMM MMM MMM MMM MMMCatalyst weight, gm 120.5 120.5 120.5 120.5 120.5 120.5 120.5 120.5Pressure, psig 600 600 600 600 600 600 600 600Temperature, .degree.C. 268 273 300 301 302 301 302 301Time on organics, hrs. 5.0 21.0 27.5 45.0 47.0 55.0 68.0 71.0Duration of run, hrs. 2 16 2 15 2 2 13 3MEA SV, gmol/hr/kgcat 1.93 2.17 1.86 1.93 1.92 1.65 1.68 1.72NH.sub.3 feedrate, gm/hr 77.0 57.7 51.5 53.0 51.5 51.5 46.4 48.7Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 -- -- --AEEA -- -- -- -- -- 33.54 33.54 33.54Liquid product composition,wt. %EDA 0.46 0.36 1.97 1.71 1.80 1.01 1.10 1.04MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 8.19 8.94 3.30 4.02 4.32 0.00 0.00 0.00EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.71 0.58 1.70 1.53 1.45 8.12 8.21 8.14DETA 81.58 82.37 80.61 82.51 85.17 78.02 81.61 78.10AEEA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00AEP 0.77 0.66 1.96 1.66 1.50 1.16 1.11 1.10HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 7.44 6.50 8.97 6.92 4.84 5.71 4.32 5.58TEPA's 0.73 0.49 0.59 0.26 0.00 5.01 3.31 4.78ROH Conversion % 65.18 61.92 86.01 82.82 81.58 100.00 100.00 100.00Acyclic (N4)/cyclic (< = N4), 100.00 100.00 12.60 15.50 100.00 0.10 0.00 0.10weight ratioAcyclic (N5)/cyclic (< = N5), 100.00 100.00 100.00 100.00 -- 25.20 100.00 20.90weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- 0.90 0.80 0.86weight ratio__________________________________________________________________________ TABLE LVIII__________________________________________________________________________Example No. 538 539 540 541 542 543 544 545 546 547 548 549__________________________________________________________________________Catalyst Type NNN NNN NNN NNN NNN NNN NNN NNN NNN NNN NNN NNNCatalyst weight, gm 119.6 119.6 119.6 119.6 119.6 119.6 119.6 119.6 119.6 119.6 119.6 119.6Pressure, psig 600 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 272 274 273 299 301 300 273 300 298 299 272 275Time on organics, hrs. 4.0 20.0 22.0 27.0 44.0 46.0 49.0 66.0 68.0 70.0 74.0 86.0Duration of run, hrs. 2 16 2 2 16 2 2 16 2 2 3 3MEA SV, gmol/hr/kgcat 2.01 2.16 2.02 1.93 1.94 2.01 1.99 1.71 1.73 1.65 1.71 1.15NH.sub.3 feedrate, gm/hr 47.0 46.5 53.5 44.0 60.8 50.5 59.0 45.2 56.5 56.5 64.0 59.4Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- -- 22.84AEEA -- -- -- -- -- -- -- 33.54 33.54 33.54 33.54 --Liquid product composition,wt. %EDA 0.00 0.00 0.00 2.00 1.82 1.80 0.00 1.63 1.66 1.44 0.00 0.00MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 6.84 7.07 7.00 2.75 2.63 2.57 8.52 0.00 0.00 0.00 0.00 9.35EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.21 0.85 0.69 1.96 2.02 2.11 0.58 9.79 10.05 10.16 6.52 0.72DETA 83.64 87.98 88.48 83.40 82.22 81.77 87.13 75.36 72.92 72.45 80.94 83.87AEEA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.47 0.00AEP 1.32 0.82 0.72 2.56 2.51 2.55 0.69 1.93 1.98 1.88 0.57 0.69HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 6.59 3.27 3.11 6.33 7.56 7.85 3.08 7.07 7.66 7.60 3.57 4.14TEPA's 0.41 0.00 0.00 0.00 0.56 0.71 0.00 3.95 4.60 5.08 4.74 0.51ROH Conversion % 71.08 69.97 70.25 88.33 88.90 89.16 63.70 100.00 100.00 100.00 89.80 59.87Acyclic (N4)/cyclic (< = 100.00 100.00 100.00 14.10 7.74 7.62 100.00 0.00 0.18 0.17 0.00 0.00N4), weight ratioAcyclic (N5)/cyclic (< = 100.00 0.00 00.00 0.00 0.00 0.00 0.00 11.00 9.80 11.09 100.00 100.00N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- -- 0.60 0.60 0.70 1.30 --weight ratio__________________________________________________________________________ TABLE LIX__________________________________________________________________________Example No. 550 551 552 553 554 555 556 557 558 559 560__________________________________________________________________________Catalyst Type OOO OOO OOO OOO OOO OOO OOO OOO OOO OOO OOOCatalyst weight, gm 119.0 119.0 119.0 119.0 119.0 119.0 119.0 119.0 119.0 119.0 119.0Pressure, psig 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 272 271 272 293 293 293 293 290 292 270 270Time on organics, hrs. 6.0 22.0 24.0 29.0 46.0 48.0 53.0 69.5 71.5 76.5 93.0Duration of run, hrs. 2 16 2 2 16 2 2 15 2 2 16MEA SV, gmol/hr/kgcat 1.91 1.91 1.92 1.87 1.87 1.92 1.56 1.58 1.50 1.66 1.69NH.sub.3 feedrate, gm/hr 50.0 45.0 51.0 61.0 52.0 63.5 65.0 47.8 50.5 45.0 68.6Liquid feed composition,wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- -- 22.84AEEA -- -- -- -- -- -- 33.54 33.54 33.54 33.54 --Liquid product composition,wt. %EDA 0.63 0.69 0.72 2.72 3.02 2.99 2.68 3.21 3.67 0.60 0.78MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 15.06 14.67 14.70 7.20 6.66 6.83 0.37 0.24 0.24 0.45 14.81EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.51 0.58 0.59 1.88 2.08 2.11 6.78 7.42 7.73 4.42 1.25DETA 76.49 75.73 75.87 69.26 69.03 67.89 61.99 60.81 59.19 65.18 71.26AEEA 0.75 0.79 0.78 0.17 0.00 0.21 0.24 0.16 0.00 10.62 1.89AEP 0.53 0.59 0.60 2.19 2.37 2.41 2.12 2.49 2.81 0.51 0.71HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 4.07 4.50 4.48 9.01 9.15 8.99 8.99 9.15 9.40 4.16 5.02TEPA's 1.66 1.99 1.94 5.81 5.97 6.10 12.71 11.71 12.96 12.13 3.62ROH Conversion % 35.01 36.68 36.63 69.16 71.53 70.57 99.30 99.50 100.00 68.50 36.13Acyclic (N4)/cyclic (< = 100.00 40.70 32.30 4.40 4.00 4.20 0.67 0.30 0.30 0.10 5.00N4), weight ratioAcyclic (N5)/cyclic (< = 100.00 100.00 100.00 2.90 2.40 2.50 2.50 1.90 1.10 21.70 100.00N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 1.40 1.30 1.40 2.90 --weight ratio__________________________________________________________________________ TABLE LX__________________________________________________________________________Example No. 561 562 563 564 565 566 567__________________________________________________________________________Catalyst Type PPP PPP PPP PPP PPP PPP PPPCatalyst weight, gm 113.7 113.7 113.7 113.7 113.7 113.7 113.7Pressure, psig 600 600 600 600 600 600 600Temperature, .degree.C. 274 274 299 299 303 294 297Time on organics, hrs. 18.0 20.0 25.0 41.7 43.4 49.0 65.5Duration of run, hrs. 16 2 2 16 2 2 16MEA SV, gmol/hr/kgcat 2.15 2.19 2.20 2.10 2.19 2.11 2.14NH.sub.3 feedrate, gm/hr 55.6 43.0 52.0 55.0 38.0 84.0 52.0Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 73.30 73.30MEA 22.84 22.84 22.84 22.84 22.84 21.70 21.70EDA -- -- -- -- -- -- --H.sub.2 O -- -- -- -- -- 5.00 5.00Liquid product composition,wt. %EDA 0.85 0.69 2.50 1.60 1.42 1.28 1.24MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 11.05 11.08 3.45 6.52 7.59 10.77 11.01EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.46 0.37 1.22 0.77 0.70 0.53 0.50DETA 71.01 72.32 65.63 70.92 72.86 73.67 73.65AEEA 1.08 1.21 0.25 0.59 0.78 0.94 1.06AEP 0.69 0.56 2.04 1.27 1.14 0.99 0.93HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 11.09 10.78 15.98 11.82 10.35 8.14 8.13TEPA's 2.74 2.32 5.41 3.35 2.60 1.92 1.81ROH Conversion % 52.50 52.51 85.08 71.61 67.04 53.28 52.25Acyclic (N4)/cyclic (< = N4), 30.30 100.00 9.50 13.90 13.00 17.80 19.80weight ratioAcyclic (N5)/cyclic (< = N5), 31.60 100.00 6.70 10.00 13.40 12.90 31.20weight ratio.SIGMA.(N5)/.SIGMA.(N4), 14.70 10.50 5.30 7.10 7.60 8.00 8.70weight ratio__________________________________________________________________________Example No. 568 569 570 571 572 573 574__________________________________________________________________________Catalyst Type PPP PPP PPP PPP PPP PPP PPPCatalyst weight, gm 113.7 113.7 113.7 113.7 113.7 113.7 113.7Pressure, psig 600 600 600 600 600 600 600Temperature, .degree.C. 293 299 298 297 300 298 298Time on organics, hrs. 67.4 72.4 89.5 91.5 112.2 114.2 149.2Duration of run, hrs. 2 2 16 2 15 2 2MEA SV, gmol/hr/kgcat 2.06 2.09 2.07 2.08 3.06 3.17 11.03NH.sub.3 feedrate, gm/hr 54.0 47.0 67.0 49.5 57.0 54.0 47.0Liquid feed composition, wt. %DETA 73.30 77.16 77.16 77.16 -- -- --MEA 21.70 22.84 22.84 22.84 33.70 33.70 100.00EDA -- -- -- -- 66.30 66.30 --H.sub.2 O 5.00 -- -- -- -- -- --Liquid product composition,wt. %EDA 1.16 1.17 1.09 1.06 69.42 67.49 1.37MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 11.46 9.15 10.15 10.62 20.41 20.60 85.05EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.46 0.52 0.44 0.40 0.54 0.53 0.51DETA 74.18 72.91 74.49 75.62 4.65 6.35 1.42AEEA 1.07 1.21 1.18 1.20 2.23 2.29 8.02AEP 0.88 0.90 0.83 0.80 0.62 0.62 0.58HEP 0.00 0.06 0.00 0.00 0.00 0.00 0.39TETA's 7.51 8.79 7.76 6.81 1.00 1.04 0.51TEPA's 1.57 2.10 1.50 1.19 0.11 0.82 0.00ROH Conversion % 50.21 59.84 55.60 53.59 40.05 35.71 15.17Acyclic (N4)/cyclic (< = N4), 21.10 14.70 15.60 18.70 -- -- --weight ratioAcyclic (N5)/cyclic (< = N5), 14.90 21.40 100.00 100.00 -- -- --weight ratio.SIGMA.(N5)/.SIGMA.(N4), 9.00 7.60 8.10 8.70 -- -- --weight ratio__________________________________________________________________________ TABLE LXI__________________________________________________________________________Example No. 575 576 577 578 579 580 581__________________________________________________________________________Catalyst Type QQQ QQQ QQQ QQQ QQQ QQQ QQQCatalyst weight, gm 123.1 123.1 123.1 123.1 123.1 123.1 123.1Pressure, psig 600 600 600 600 600 600 600Temperature, .degree.C. 278 280 279 308 306 305 305Time on organics, hrs. 31.2 19.5 21.5 26.2 32.2 49.2 51.2Duration of run, hrs. 1 16 2 2 2 16 2MEA SV, gmol/hr/kgcat 2.14 1.96 1.95 1.93 1.91 1.64 1.65NH.sub.3 feedrate, gm/hr 80.0 53.0 53.5 58.5 59.5 56.0 47.0Liquid feed composition,wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 -- --AEEA -- -- -- -- -- 33.54 33.54Liquid product composition,wt. %EDA 0.93 0.49 0.46 1.74 1.34 1.17 1.12MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 15.52 14.20 14.55 7.82 10.95 0.58 0.25EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.08 0.13 0.11 0.66 0.36 4.33 4.26DETA 79.78 80.09 80.45 79.71 78.22 72.69 71.85AEEA 0.63 0.82 0.84 0.58 0.97 4.41 5.88AEP 0.38 0.42 0.39 1.19 0.85 0.97 0.80HEP 0.00 0.00 0.00 0.00 0.12 0.15 0.08TETA's 2.32 3.12 2.68 6.54 3.78 8.89 8.53TEPA's 0.00 0.22 0.16 1.09 0.55 4.30 4.08ROH Conversion % 32.65 38.51 37.03 65.50 51.72 86.80 82.30Acyclic (N4)/cyclic (< = N4), -- -- 100.00 11.57 12.90 7.79 10.00weight ratioAcyclic (N5)/cyclic (< = N5), -- -- -- -- -- 0.10 0.10weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- 0.50 0.50weight ratio__________________________________________________________________________ TABLE LXII__________________________________________________________________________Example No. 582 583 584 585 586 587 588 589__________________________________________________________________________Catalyst Type RRR RRR RRR RRR RRR RRR RRR RRRCatalyst weight, gm 116.4 116.4 116.4 116.4 116.4 116.4 116.4 116.4Pressure, psig 600 600 600 600 600 600 600 600Temperature, .degree.C. 274 274 274 303 301 303 301 301Time on organics, hrs. 3.0 18.8 20.8 26.5 43.0 45.0 50.4 55.1Duration of run, hrs. 1 16 2 2 16 2 2 2MEA SV, gmol/hr/kgcat 2.05 2.07 2.11 2.03 2.02 1.97 3.24 3.26NH.sub.3 feedrate, gm/hr 70.0 60.3 53.5 93.0 60.8 61.0 53.0 78.5Liquid feed composition,wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 62.81 62.81MEA 22.84 22.84 22.84 22.84 22.84 22.84 37.19 37.19Liquid product composition,wt %EDA 1.07 1.05 0.86 3.00 2.27 1.97 2.25 1.86MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 10.34 10.06 11.47 3.86 6.06 7.28 15.71 21.10EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.07 0.69 0.44 1.44 1.06 0.87 1.14 0.71DETA 71.40 71.74 74.72 68.70 70.45 72.29 62.19 63.50AEEA 2.14 1.02 1.02 0.29 0.47 0.62 1.27 1.68AEP 1.05 0.89 0.63 2.17 1.54 1.30 1.61 1.01HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 8.90 10.65 8.62 13.51 11.60 10.01 9.86 5.67TEPA's 3.00 2.71 1.52 3.58 2.99 2.10 2.09 1.32ROH Conversion % 55.63 56.77 50.69 83.26 73.52 68.05 57.95 43.18Acyclic (N4)/cyclic (< = N4), 14.20 26.00 40.00 7.30 9.40 11.10 8.40 13.00weight ratioAcyclic (N5)/cyclic (< = N5), 21.70 25.90 100.00 3.90 5.60 26.00 13.70 2.97weight ratio.SIGMA.(N5)/.SIGMA.(N4), 5.00 9.50 13.00 3.90 -- -- 4.00 4.70weight ratio__________________________________________________________________________ TABLE LXIII__________________________________________________________________________Example No. 590 591 592 593 594 595 596 597 598 599 600 601__________________________________________________________________________Catalyst Type SSS SSS SSS SSS SSS SSS SSS SSS SSS SSS SSS SSSCatalyst weight, gm 105.1 105.1 105.1 105.1 105.1 105.1 105.1 105.1 105.1 105.1 105.1 105.1Pressure, psig 600 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 284 286 284 304 303 276 276 280 306 311 311 311Time on organics, hrs. 3.0 19.0 20.0 41.6 43.6 49.0 65.0 67.0 71.0 78.0 92.0 94.0Duration of run, hrs. 1 16 2 16 2 2 15 2 2 2 2 2MEA SV, gmol/hr/kgcat 2.30 2.34 2.35 2.26 2.29 2.00 1.97 1.94 1.96 1.84 1.90 1.98NH.sub.3 feedrate, gm/hr 60.5 59.0 52.5 53.4 56.5 54.5 61.5 54.0 48.0 63.0 45.0 53.0Liquid feed composition,wt. %EDA -- -- -- -- -- -- -- -- -- 18.29 18.29 18.29DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46 31.41 31.41 31.41MEA 22.84 22.84 22.84 22.84 22.84 -- -- -- -- 18.59 18.59 18.59AEEA -- -- -- -- -- 33.54 33.54 33.54 33.54 31.71 31.71 31.71Liquid product compo-sition, wt. %EDA 1.42 1.51 1.58 4.01 4.05 0.68 0.62 0.57 3.04 27.12 23.79 25.27MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 9.68 8.49 9.09 3.41 3.82 0.36 0.19 0.16 0.00 3.52 3.25 3.40EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.16 1.29 1.28 2.99 2.95 6.65 6.30 5.94 9.68 10.98 9.83 10.11DETA 71.42 70.10 71.52 65.54 64.54 71.47 69.54 69.17 57.76 28.16 27.11 27.67AEEA 0.59 0.59 0.55 0.23 0.18 8.21 9.71 10.06 0.27 0.42 0.37 0.33AEP 1.08 1.25 1.22 3.33 3.12 0.89 0.75 0.73 3.14 6.78 7.24 6.99HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 11.29 12.78 11.42 13.94 14.12 4.16 3.83 3.84 11.05 12.22 14.47 13.61TEPA's 2.65 3.21 2.53 3.96 4.53 6.84 8.00 8.60 10.52 6.38 7.75 7.53ROH Conversion % 58.68 63.87 61.20 85.42 83.62 75.90 71.50 70.50 99.20 81.42 82.82 81.99Acyclic (N4)/cyclic 28.50 26.30 26.00 6.70 6.80 0.40 0.30 0.30 0.50 0.90 0.90 0.90(< = N4), weight ratioAcyclic (N5)/cyclic -- -- 100.00 4.10 4.00 61.00 79.00 28.20 4.10 0.70 0.80 0.80(< = N5), weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- 1.64 2.10 2.20 1.00 -- -- --weight ratio__________________________________________________________________________ TABLE LXIV__________________________________________________________________________Example No. 602 603 604 605 606 607 608 609 610 611 612__________________________________________________________________________Catalyst Type TTT TTT TTT TTT TTT TTT TTT TTT TTT TTT TTTCatalyst weight, gm 117.9 117.9 117.9 117.9 117.9 117.9 117.9 117.9 117.9 117.9 117.9Pressure, psig 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 278 277 301 302 301 300 300 303 301 302 302Time on organics, hrs. 18.0 20.0 25.0 40.0 42.0 47.5 65.5 87.0 88.5 109.0 111.0Duration of run, hrs. 16 2 2 14 2 2 2 19 2 20 2MEA SV, gmol/hr/kgcat 2.03 2.06 1.98 2.00 2.11 1.74 1.32 3.51 3.79 3.30 3.45NH.sub.3 feedrate, gm/hr 56.0 54.0 54.0 63.0 61.0 60.0 10.0 67.8 54.0 67.9 48.5Liquid feed composition,wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 62.81 62.81 62.81 62.81MEA 22.84 22.84 22.84 22.84 22.84 -- -- 37.19 37.19 37.19 37.19AEEA -- -- -- -- -- 33.54 33.54 -- -- -- --Liquid product composition,wt. %EDA 1.02 0.88 3.46 2.84 2.51 1.46 2.23 2.44 2.31 2.15 2.01MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 12.18 11.85 5.47 5.76 6.66 0.35 0.15 15.93 16.51 17.85 18.61EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.50 0.49 1.74 1.49 1.27 5.41 5.82 1.39 1.23 1.13 1.02DETA 74.13 74.56 70.50 71.81 70.37 70.92 61.30 60.00 61.02 61.91 62.27AEEA 1.14 1.11 0.39 0.48 0.56 3.78 4.31 1.92 1.89 2.00 2.10AEP 0.64 0.64 2.16 1.91 1.65 1.24 2.04 1.64 1.58 1.42 1.26HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 7.19 7.69 10.84 10.30 10.16 6.34 7.31 9.54 9.36 8.29 8.01TEPA's 2.28 1.79 2.96 2.74 3.47 8.47 12.87 3.31 2.80 2.39 2.35ROH Conversion % 47.45 48.87 76.39 75.07 70.93 88.80 87.00 57.42 56.04 52.52 50.66Acyclic (N4)/cyclic (< = N4), 30.70 29.40 6.40 7.90 8.10 0.30 0.50 6.70 6.40 8.40 9.20weight ratioAcyclic (N5)/cyclic (< = N5), 2.70 100.00 3.50 4.40 5.20 11.70 12.20 4.70 3.90 4.80 5.10weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- 1.30 1.80 -- -- -- --weight ratio__________________________________________________________________________ TABLE LXV__________________________________________________________________________Example No. 613 614 615 616 617 618 619 620 621__________________________________________________________________________Catalyst Type UUU UUU UUU UUU UUU UUU UUU UUU UUUCatalyst weight, gm 116.4 116.4 116.4 116.4 116.4 116.4 116.4 116.4 116.4Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 278 291 278 304 307 306 301 302 302Time on organics, hrs. 18.0 20.2 22.2 28.0 44.5 46.5 55.5 68.5 70.5Duration of run, hrs. 16 16 2 2 16 2 2 13 2MEA SV, gmol/hr/kgcat 2.03 2.05 2.06 2.07 2.00 2.02 1.73 1.72 1.78NH.sub.3 feedrate, gm/hr 56.0 51.2 51.5 56.0 56.0 53.5 64.0 59.7 59.7Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- --AEEA -- -- -- -- -- -- 33.54 33.54 33.54Liquid product composition,wt. %EDA 1.02 1.12 0.70 2.22 2.31 2.54 1.67 1.70 1.86MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 12.18 10.60 11.71 6.34 6.10 6.24 0.21 0.00 0.20EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.50 0.56 0.35 1.18 1.19 1.22 7.01 6.71 7.26DETA 74.13 76.35 76.18 74.45 74.51 74.81 73.57 73.53 73.22AEEA 1.14 0.90 1.00 0.49 0.42 0.43 1.39 1.52 1.41AEP 0.64 0.79 0.61 1.53 1.60 1.58 1.22 1.17 1.15HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 7.19 7.58 7.18 9.57 8.76 8.18 7.33 7.38 7.12TEPA's 2.28 1.36 1.47 1.86 3.57 1.80 4.61 5.25 4.68ROH Conversion % 47.45 54.45 49.55 72.57 73.87 72.74 95.90 95.50 95.80Acyclic (N4)/cyclic (< = N4), 30.70 24.30 30.50 11.20 10.20 8.90 0.20 0.10 0.10weight ratioAcyclic (N5)/cyclic (< = N5), 2.70 100.00 100.00 10.00 5.80 7.40 11.80 9.80 11.00weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 0.60 0.70 0.70weight ratio__________________________________________________________________________ TABLE LXVI__________________________________________________________________________Example No. 622 623 624 625 626 627 628 629__________________________________________________________________________Catalyst Type VVV VVV VVV VVV VVV VVV VVV VVVCatalyst weight, gm 117.2 117.2 117.2 117.2 117.2 117.2 117.2 117.2Pressure, psig 600 600 600 600 600 600 600 600Temperature, .degree.C. 276 277 275 299 290 302 300 308Timer on organics, hrs. 4.0 11.0 20.0 26.0 36.0 40.0 45.0 57.0Duration of run, hrs. 2 2 2 2 10 2 2 2MEA SV, gmol/hr/kgcat 1.76 2.31 2.08 2.00 2.03 1.95 1.81 1.69NH.sub.3 feedrate, gm/hr 29.0 37.5 58.0 55.0 55.0 52.0 59.0 49.5Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- --AEEA -- -- -- -- -- -- 33.54 33.54Liquid product composition,wt. %EDA 1.54 1.38 1.38 2.84 2.73 3.56 1.85 2.20MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 8.33 7.66 13.37 5.58 5.61 6.07 0.33 0.00EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 1.26 1.16 0.29 1.49 1.48 1.46 7.47 6.84DETA 74.34 74.58 80.12 74.81 70.27 70.19 71.84 71.91AEEA 1.27 0.89 0.00 0.00 0.00 0.13 1.65 1.10AEP 0.64 1.29 0.54 1.97 1.90 1.84 1.31 1.68HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 10.00 10.98 4.25 10.18 11.99 10.45 5.91 6.40TEPA's 2.07 1.86 0.00 1.74 3.50 2.98 7.79 6.50ROH Conversion % 64.49 67.56 42.44 76.15 75.80 73.51 95.10 96.70Acyclic (N4)/cyclic (< = N4), 17.80 20.40 20.40 9.50 11.40 9.80 0.20 0.30weight ratioAcyclic (N5)/cyclic (< = N5), -- -- -- 5.30 7.30 -- 22.60 11.20weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 1.30 1.00weight ratio__________________________________________________________________________ TABLE LXVII__________________________________________________________________________Example No. 630 631 632 633 634 635 636 637__________________________________________________________________________Catalyst Type WWW WWW WWW WWW WWW WWW WWW WWWCatalyst weight, gm 107.3 107.3 107.3 107.3 107.3 107.3 107.3 107.3Pressure, psig 600 600 600 600 600 600 600 600Temperature, .degree.C. 276 275 276 300 301 300 301 301Time on organics, hrs. 4.0 14.0 16.0 21.0 37.5 39.5 47.5 44.0Duration of run, hrs. 2 10 2 2 16 2 2 2MEA SV, gmol/hr/kgcat 2.22 2.22 2.28 2.18 2.06 1.92 1.90 1.82NH.sub.3 feedrate, gm/hr 49.0 53.7 51.0 49.0 52.3 60.0 61.0 49.5Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 -- -- --AEEA -- -- -- -- -- 33.54 33.54 33.54Liquid product composition,wt. %EDA 0.59 0.48 0.42 1.39 1.39 1.17 1.18 1.35MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 11.78 12.64 12.69 7.30 8.85 0.48 0.00 8.79EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.32 0.18 0.14 0.65 0.57 5.50 5.68 0.57DETA 81.41 81.70 81.91 81.16 82.83 79.81 81.98 84.88AEEA 1.12 0.89 0.89 0.00 0.00 2.01 1.94 1.08AEP 0.57 0.50 0.48 1.17 1.08 1.14 1.08 0.00HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 3.71 3.08 2.89 5.97 3.52 6.18 5.18 1.83TEPA's 0.00 0.00 0.00 0.65 0.00 1.97 1.34 0.00ROH Conversion % 49.22 45.39 45.13 68.46 61.55 94.00 94.20 96.70Acyclic (N4)/cyclic (< = N4), 100.00 100.00 100.00 25.40 18.40 100.00 100.00 100.00weight ratioAcyclic (N5)/cyclic (< = N5), -- -- -- 100.00 -- 0.00 0.00 --weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- 0.30 0.30 --weight ratio__________________________________________________________________________ TABLE LXVIII__________________________________________________________________________Example No. 638 639 640 641 642 643 644 645__________________________________________________________________________Catalyst Type XXX XXX XXX XXX XXX XXX XXX XXXCatalyst weight, gm 126.9 126.9 126.9 126.9 126.9 126.9 126.9 126.9Pressure, psig 600 600 600 600 600 600 600 600Temperature, .degree.C. 282 264 269 296 283 290 299 272Time on organics, hrs. 4.0 24.0 27.0 48.0 50.0 67.5 69.5 75.0Duration of run, hrs. 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 1.87 1.84 1.86 1.71 1.87 1.63 1.67 1.64NH.sub.3 feedrate, gm/hr 53.5 54.0 51.0 55.0 50.0 45.0 41.0 51.0Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46MEA 22.84 22.84 22.84 22.84 22.84 -- -- --AEEA -- -- -- -- -- 33.54 33.54 33.54Liquid product composition,wt. %EDA 2.60 1.08 0.73 2.34 1.57 1.64 1.62 0.00MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 2.38 8.61 10.46 5.48 7.30 0.00 0.00 0.00EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 2.30 0.91 0.71 2.12 1.59 11.97 12.36 6.27DETA 72.97 78.50 79.50 76.30 78.68 68.16 71.00 77.31AEEA 0.00 0.00 0.00 0.00 0.00 1.42 1.38 14.18AEP 3.04 1.12 0.68 2.28 1.55 1.79 1.72 0.47HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 13.55 7.63 6.79 7.81 7.22 8.73 7.12 1.57TEPA's 3.04 1.60 0.92 1.88 1.11 4.32 3.21 0.00ROH Conversion % 90.08 63.26 55.30 76.51 68.80 95.90 96.00 58.30Acyclic (N4)/cyclic (< = N4), 7.10 10.50 100.00 5.40 9.90 0.10 0.00 0.00weight ratioAcyclic (N5)/cyclic (< = N5), 7.80 100.00 100.00 2.90 100.00 10.50 100.00 100.00weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- 0.50 0.50 --weight ratio__________________________________________________________________________ TABLE LXIX__________________________________________________________________________Example No. 646 647 648 649 650 651 652 653 654 655 656__________________________________________________________________________Catalyst Type YYY YYY YYY YYY YYY YYY YYY YYY YYY YYY YYYCatalyst weight, gm 120.2 120.2 120.2 120.2 120.2 120.2 120.2 120.2 120.2 120.2 120.2Pressure, psig 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 272 273 273 289 300 299 297 300 299 272 272Time on organics, hrs. 3.5 19.5 21.5 27.5 43.5 45.5 50.5 66.5 68.5 70.5 73.5Duration of run, hrs. 2 16 2 2 16 2 2 16 2 2 1MEA SV, gmol/hr/kgcat 1.92 1.95 2.06 2.09 1.94 1.99 1.56 1.58 1.55 1.66 2.03NH.sub.3 feedrate, gm/hr 111.0 50.9 66.0 80.0 58.0 55.0 68.0 64.5 84.8 67.0 49.0Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- -- 22.84AEEA -- -- -- -- -- -- 33.54 33.54 33.54 33.54 --Liquid product composition,wt. %EDA 0.00 0.00 0.00 0.00 1.08 0.00 0.00 0.00 0.00 0.00 0.00MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 8.22 8.33 7.82 2.98 3.36 3.69 1.08 1.14 0.00 0.00 9.79EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.00 0.00 0.00 0.91 0.73 0.71 5.15 4.86 4.64 3.87 0.43DETA 88.30 87.01 88.01 84.49 81.52 83.00 83.96 79.07 83.12 84.96 87.16AEEA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.65 0.73 5.72 0.00AEP 0.37 0.38 0.38 1.42 1.30 1.22 1.35 1.06 1.01 0.43 0.49HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 3.10 4.29 3.79 8.95 10.19 8.57 4.93 6.53 5.81 2.15 2.13TEPA's 0.00 0.00 0.00 0.75 1.14 0.79 2.69 5.45 4.13 2.87 0.00ROH Conversion % 64.92 64.48 66.67 87.43 85.77 84.16 99.30 99.50 100.00 68.50 58.15Acyclic (N4)/cyclic (< = N4), 100.00 100.00 100.00 26.20 17.50 17.80 0.31 0.10 0.06 0.00 100.00weight ratioAcyclic (N5)/cyclic (< = N5), -- -- -- 100.00 100.00 100.00 100.00 22.20 100.00 100.00 --weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- -- -- -- -- --weight ratio__________________________________________________________________________ TABLE LXX__________________________________________________________________________Example No. 657 658 659 660 661 662 663 664 665 666 667__________________________________________________________________________Catalyst Type ZZZ ZZZ ZZZ ZZZ ZZZ ZZZ ZZZ ZZZ ZZZ ZZZ ZZZCatalyst weight, gm 116.3 116.3 116.3 116.3 116.3 116.3 116.3 116.3 116.3 116.3 116.3Pressure, psig 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 275 275 275 300 303 300 299 299 300 274 275Time on organics, hrs. 6.0 23.0 25.0 29.0 47.0 49.0 54.0 71.0 73.0 78.0 95.0Duration of run, hrs. 2 16 2 2 16 2 2 17 2 2 16MEA SV, gmol/hr/kgcat 1.92 2.00 2.03 1.96 1.96 1.95 1.74 1.51 1.60 1.78 1.99NH.sub.3 feedrate, gm/hr 70.0 61.1 57.5 49.5 51.3 52.0 55.5 48.8 50.5 55.0 48.3Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 66.46 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- -- 22.84AEEA -- -- -- -- -- -- 33.54 33.54 33.54 33.54 --Liquid product composition,wt. %EDA 1.09 0.80 0.74 1.86 1.69 1.60 1.45 1.55 1.62 0.58 0.58MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 13.57 15.03 15.47 8.52 10.49 11.24 0.62 0.38 0.38 0.46 16.94EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.34 0.20 0.18 0.56 0.47 0.42 3.49 3.53 3.46 1.39 0.14DETA 71.01 74.43 74.82 71.47 73.78 74.30 72.62 70.62 71.21 69.66 76.98AEEA 1.11 1.21 1.24 0.65 0.87 0.99 4.28 4.09 4.36 20.93 2.65AEP 0.51 0.33 0.31 0.91 0.77 0.73 0.76 0.68 0.67 0.22 0.25HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 7.40 5.81 5.25 8.79 6.82 5.83 6.63 6.99 6.60 1.40 1.67TEPA's 3.76 1.88 1.60 4.50 2.87 2.23 8.06 8.11 7.70 4.25 0.37ROH Conversion % 41.20 35.13 33.09 62.86 54.23 50.62 87.20 87.50 86.70 37.40 26.29Acyclic (N4)/cyclic (< = N4), 24.50 100.00 100.00 12.00 12.80 11.60 0.12 0.10 0.10 0.10 100.00weight ratioAcyclic (N5)/cyclic (< =N5), 9.60 100.00 100.00 5.90 8.70 17.10 10.20 11.50 12.70 100.00 100.00weight ratio.SIGMA.(N5)/.SIGMA.(N4), -- -- -- -- -- -- 1.20 1.20 1.20 3.00 --weight ratio__________________________________________________________________________ TABLE LXXI__________________________________________________________________________Example No. 668 669 670 671 672 673 674 675 676 677 678__________________________________________________________________________Catalyst Type AAAA AAAA AAAA AAAA AAAA AAAA AAAA AAAA AAAA AAAA AAAACatalyst weight, gm 117.7 117.7 117.7 117.7 117.7 117.7 117.7 117.7 117.7 117.7 117.7Pressure, psig 600 600 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 275 275 277 303 302 302 273 301 301 274 274Time on organics, hrs. 6.0 22.0 24.0 29.0 45.6 47.6 52.6 69.7 71.7 76.7 93.7Duration of run, hrs. 2 16 2 2 16 2 2 16 2 2 16MEA SV, gmol/hr/kgcat 1.98 1.99 2.03 1.99 1.99 2.03 2.00 1.58 1.70 1.75 1.98NH.sub.3 feedrate, gm/hr 68.0 54.3 50.5 55.5 47.8 48.5 79.0 68.3 72.5 79.5 68.1Liquid feed composition, wt. %DETA 77.16 77.16 77.16 77.16 77.16 77.16 77.16 66.46 66.46 66.46 77.16MEA 22.84 22.84 22.84 22.84 22.84 22.84 22.84 -- -- -- 22.84AEEA -- -- -- -- -- -- -- 33.54 33.54 33.54 --Liquid product composition,wt. %EDA 0.97 0.91 0.90 2.63 2.07 1.73 0.53 1.35 1.32 0.42 0.48MeEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00MEA 11.59 11.42 11.61 3.72 5.41 7.22 15.50 0.39 0.26 0.39 15.13EtEDA 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00PIP 0.35 0.33 0.31 0.84 0.64 0.53 0.12 3.59 3.54 1.45 0.22DETA 71.40 70.89 71.27 67.56 69.33 71.24 76.04 68.79 68.37 66.67 74.89AEEA 1.15 1.26 1.28 0.23 0.44 0.85 1.39 2.48 3.15 20.08 3.01AEP 0.52 0.49 0.47 1.53 1.12 0.91 0.30 0.81 0.69 0.23 0.29HEP 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00TETA's 9.08 9.52 9.30 12.67 11.55 9.77 4.68 6.58 6.06 1.62 3.65TEPA's 4.20 4.41 4.17 7.89 6.69 5.30 1.17 13.35 12.33 7.56 1.63ROH Conversion % 50.26 51.01 50.20 83.98 76.63 68.73 33.00 92.60 90.40 39.90 34.34Acrylic (N4)/cyclic (< = N4), 38.80 46.80 50.10 9.60 13.90 17.20 100.00 0.30 0.20 0.20 15.70weight ratioAcrylic (N5)/cyclic (< = N5), 21.00 24.40 22.90 4.10 6.10 8.90 100.00 13.50 16.00 100.00 8.20weight ratio.SIGMA.(N5)/.SIGMA.(N4)), -- -- -- -- -- -- -- 2.00 12.00 4.70 --weight ratio__________________________________________________________________________ TABLE LXXII__________________________________________________________________________Example No. 679 680 681 682 683 684 685 686 687 688 689 690__________________________________________________________________________Catalyst Type BBBB BBBB BBBB BBBB BBBB BBBB BBBB BBBB BBBB BBBB BBBB BBBBCatalyst weight, gm 78.74 78.74 78.74 78.74 78.74 78.74 78.74 78.74 78.74 78.74 78.74 78.74Pressure, psig 606 603 603 602 603 603 603 598 603 603 604 603Temperature,.degree.C. 270 270 280 269 259 280 280 270.1 270 280 259 269Time on organics, hrs. 4.5 4.5 28.5 51.5 71.5 76.5 100.5 120 167.5 172.5 191.5 196.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.46 3.84 3.94 3.87 3.77 3.63 3.78 3.83 3.81 3.71 3.89 3.89DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition,wt. %EDA 0.874 1.232 1.585 0.847 0.433 1.400 1.565 0.773 0.551 1.445 0.461 0.791MEA 12.473 11.945 7.517 13.370 17.877 6.436 7.199 12.823 16.111 5.976 18.787 12.858PIP 0.965 1.116 1.414 1.070 0.651 1.400 1.451 1.028 0.807 1.387 0.691 1.023DETA 39.228 39.867 35.453 41.854 47.014 35.668 35.534 41.213 44.005 33.430 47.586 40.957AEEA 1.227 1.108 0.479 1.371 2.399 0.486 0.502 1.388 1.922 0.443 2.282 1.404AEP 1.183 1.533 1.814 1.158 0.708 1.977 1.886 1.126 0.824 1.827 0.682 1.103HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.760 2.694 2.611 2.646 2.564 2.683 2.567 2.662 2.560 2.553 2.310 2.6811-TETA 12.867 13.297 13.364 12.613 12.062 14.170 13.658 12.943 12.257 13.506 10.647 12.732DAEP 0.519 0.744 0.968 0.425 0.180 0.018 0.985 0.432 0.232 1.004 0.173 0.386PEEDA 0.110 0.111 0.154 0.082 0.152 0.059 0.710 0.336 0.206 0.710 0.146 0.310DPE 0.118 0.120 0.127 0.085 0.097 0.087 0.322 0.227 0.120 0.335 0.085 0.184AE-TAEA 4.110 3.926 4.516 3.704 2.640 4.497 4.572 3.788 3.014 4.645 2.372 3.6291-TEPA 7.436 7.679 8.979 7.093 5.411 8.403 9.298 7.467 6.239 9.538 4.500 6.990AE-DAEP 0.140 0.117 0.182 0.100 0.097 0.000 0.808 0.390 0.275 0.848 0.213 0.276AE-PEEDA 0.099 0.100 0.129 0.096 0.000 0.720 0.173 0.127 0.099 0.185 0.000 0.057iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.304 0.169 0.301 0.160 0.065 0.160 1.020 0.739 0.467 1.089 0.315 0.667BPEA 0.639 0.578 0.844 0.573 0.045 0.211 1.060 0.835 0.435 1.026 0.247 0.634Others 8.068 6.841 11.264 5.414 2.775 11.735 8.190 6.222 3.695 9.232 1.904 3.598MEA conversion, % 66.60 68.06 79.87 63.84 52.17 82.68 80.79 66.20 56.64 83.70 48.64 64.40DETA conversion, % 37.56 36.64 43.59 32.72 25.25 42.94 43.64 35.44 29.62 45.82 22.68 32.60Acyclic(N4), wt. % 95.43 94.25 92.75 96.27 97.15 93.54 88.94 94.00 96.37 88.68 96.98 94.60Acyclic(N5), wt. % 90.71 92.25 90.26 92.08 97.50 92.20 81.92 84.33 87.88 81.83 89.87 86.66.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.78 0.74 0.87 0.74 0.55 0.78 0.93 0.80 0.68 0.96 0.57 0.75Acyclic(Nr)/cyclic(< = N4), 5.40 4.41 3.57 5.41 8.18 3.71 3.03 4.96 6.77 3.05 7.29 5.13weight ratio__________________________________________________________________________ Example No. 691 692 693 694 695 696__________________________________________________________________________ Catalyst Type BBBB BBBB BBBB BBBB BBBB BBBB Catalyst weight, gm 78.74 78.74 78.74 78.74 78.74 78.74 Pressure, psig 604 603 603 603 604 604 Temperature, .degree.C. 260 280 270 280 270 270 Time on organics, hrs. 214.5 219.5 238.5 243.5 262.5 266 Duration of run, hrs. 2 2 2 2 2 2 MEA SV, gmol/hr/kgcat 3.81 3.78 3.79 3.51 3.51 3.71 DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 Crude product composition, wt. % EDA 0.658 1.456 0.910 1.122 1.072 1.017 MEA 18.141 6.956 13.064 13.239 11.990 12.608 PIP 0.811 1.416 1.148 1.024 1.234 1.186 DETA 45.580 35.955 41.603 42.624 40.482 40.928 AEEA 1.879 0.493 1.322 1.350 1.216 1.269 AEP 0.881 1.832 1.184 1.192 1.267 1.191 HEP 0.000 0.000 0.000 0.000 0.000 0.000 TAEA 2.359 2.571 2.654 2.361 2.647 2.627 1-TETA 10.997 13.341 12.720 11.438 12.833 12.755 DAEP 0.275 0.888 0.410 0.490 0.472 0.422 EEDA 0.222 0.654 0.336 0.382 0.369 0.339 DPE 0.086 0.309 0.196 0.271 0.070 0.135 AE-TAEA 2.706 4.368 3.735 3.951 3.951 3.751 1-TEPA 5.378 8.945 7.412 6.576 7.610 7.246 AE-DAEP 0.183 0.700 0.300 0.385 0.331 0.291 AE-PEEDA 0.056 0.084 0.065 0.085 0.035 0.028 iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 AE-DPE 4.434 1.016 0.698 0.091 0.064 0.062 BPEA 0.403 0.932 0.638 0.093 0.594 0.053 Others 2.311 6.162 3.686 6.348 5.045 5.231 MEA conversion, % 50.59 80.69 64.55 64.31 67.22 65.36 DETA conversion, % 26.22 40.67 32.91 31.71 34.22 33.16 Acyclic(N4), wt. % 95.81 89.58 94.23 92.35 94.45 94.49 Acyclic(N5), wt. % 88.25 82.97 86.76 94.15 91.86 96.21 .SIGMA.(N5)/.SIGMA.(N4), weight 0.66o 0.90 0.79 0.75 0.77 0.70 Acyclic(N4)/cyclic(< = N4), 5.86 3.12 4.70 4.11 4.54 4.70 weight ratio__________________________________________________________________________ TABLE LXXIII__________________________________________________________________________ Example No. 697 698 699 700 701 702 703 704 705 706 707Catalyst Type CCCC CCCC CCCC CCCC CCCC CCCC CCCC CCCC CCCC CCCC CCCC__________________________________________________________________________Catalyst weight, gm 84.66 84.66 84.66 84.66 84.66 84.66 84.66 84.66 84.66 84.66 84.66Pressure, psig 598 598 598 598 598 599 599 598 603 598 598Temperature, .degree.C. 270 270 280 259 269 259 280 280 270.1 270 280Time on organics, hrs. 4.5 23.5 28.5 47.5 51.5 71.5 76.5 100.5 120 167.5 172.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2 2MEA SV, g mol/hr/kg cat 2.95 2.82 2.91 2.90 2.89 2.81 2.72 2.85 2.92 2.92 2.51DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.387 0.451 0.942 0.263 0.472 0.251 0.768 0.805 0.481 0.768 0.935MEA 18.211 18.550 12.561 24.117 18.908 22.270 11.181 11.851 17.815 11.617 9.895PIP 0.711 0.768 1.105 0.411 0.731 0.450 1.013 1.082 0.763 1.012 1.112DETA 45.762 47.529 39.025 52.023 46.902 51.519 38.122 38.925 46.516 38.660 37.291AEEA 1.902 2.077 1.192 2.582 2.111 2.804 1.247 1.088 2.005 1.321 0.909AEP 0.846 0.787 1.214 0.446 0.718 0.519 1.229 1.254 0.767 1.097 1.308HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.031 2.252 2.423 1.674 2.273 2.036 2.764 2.429 2.345 2.638 2.623l-TETA 10.921 11.106 12.012 8.125 11.140 9.812 13.613 12.691 11.657 12.643 12.534DAEP 0.186 0.202 0.477 0.080 0.175 0.097 0.523 0.523 0.191 0.461 0.560PEEDA 0.159 0.178 0.147 0.057 0.157 0.084 0.424 0.443 0.174 0.353 0.455DPE 0.084 0.096 0.095 0.052 0.114 0.086 0.094 0.303 0.105 0.353 0.332AE-TAEA 2.341 2.390 3.575 1.205 2.444 1.558 4.042 3.853 2.650 3.971 4.248l-TEPA 3.918 5.171 7.286 2.186 6.082 3.822 8.123 8.109 6.868 8.051 8.471AE-DAEP 0.366 0.189 0.131 0.129 0.081 0.000 0.417 0.508 0.093 0.479 0.536AE-PEEDA 0.080 0.079 0.101 0.068 0.000 0.000 0.113 0.139 0.000 0.163 0.150iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.403 0.061 0.264 0.051 0.078 0.066 0.220 0.797 0.055 0.793 0.918BPEA 0.328 0.276 0.649 0.076 0.291 0.128 0.215 0.930 0.371 0.949 1.033Others 6.126 2.669 9.532 1.845 2.513 1.388 8.524 7.390 2.594 7.450 7.630MEA conversion, % 51.16 50.15 66.20 34.36 49.36 40.71 70.01 68.44 52.59 68.95 73.17DETA conversion, % 27.06 24.09 37.59 15.85 25.35 18.49 39.22 38.40 26.43 38.60 39.91Acyclic(N4), wt. % 96.80 96.56 95.26 98.11 96.78 97.79 94.03 92.26 96.75 92.90 91.84Acyclic(N5), wt. % 84.17 92.59 90.47 91.27 94.99 96.53 92.65 83.44 94.83 83.45 82.83.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.56 0.59 0.79 0.37 0.65 0.46 0.75 0.87 0.69 0.88 0.93Acyclic(N4)/cyclic (< = N4), 6.52 6.58 4.75 9.37 7.08 9.58 4.99 4.20 7.00 4.66 4.02weight ratio__________________________________________________________________________ Example No. 708 709 710 711 712 713 714 715 Catalyst Type CCCC CCCC CCCC CCCC CCCC CCCC CCCC CCCC__________________________________________________________________________ Catalyst weight, gm 84.66 84.66 84.66 84.66 84.66 84.66 84.66 84.66 Pressure, psig 598 598 598 599 599 604 604 604 Temperature, .degree.C. 259 269 260 280 270 280 270 270 Time on organics, hrs. 191.5 196.5 214.5 219.5 238.5 243.5 262.5 266 Duration of run, hrs. 2 2 2 2 2 2 2 2 MEA SV, g mol/hr/kg cat 2.94 2.91 3.37 2.82 2.90 2.83 2.69 2.83 DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 Crude product composition, wt. % EDA 0.259 0.554 0.303 0.984 0.731 1.166 0.772 0.727 MEA 22.504 16.654 25.518 10.278 15.594 9.688 14.486 15.223 PIP 0.501 0.801 0.351 1.163 0.969 1.258 0.984 0.967 DETA 50.906 44.882 53.431 38.532 43.211 37.652 42.240 43.621 AEEA 2.608 1.955 2.502 0.852 1.707 0.755 1.601 1.652 AEP 0.480 0.827 0.406 1.361 1.004 1.440 1.010 0.980 HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 TAEA 2.028 2.607 1.424 2.641 2.659 2.671 2.744 2.666 l-TETA 9.067 11.734 6.423 12.393 11.936 12.701 12.439 12.081 DAEP 0.119 0.241 0.079 0.538 0.298 0.622 0.320 0.282 PEEDA 0.081 0.211 0.068 0.431 0.263 0.498 0.276 0.248 DPE 0.103 0.133 0.127 0.308 0.161 0.109 0.118 0.100 AE-TAEA 1.719 2.992 1.105 4.215 3.423 4.647 3.605 3.411 l-TEPA 3.147 5.870 1.995 8.144 6.762 8.696 6.609 6.249 AE-DAEP 0.073 0.161 0.074 0.499 0.236 0.581 0.204 0.181 AE-PEEDA 0.064 0.000 0.053 0.132 0.054 0.123 0.034 0.030 iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 AE-DPE 0.151 0.456 0.092 0.892 0.536 0.306 0.061 0.063 BPEA 0.115 0.459 0.108 0.885 0.576 0.724 0.059 0.402 Others 1.713 2.553 2.042 6.020 3.491 7.953 4.671 3.839 MEA conversion, % 39.26 54.71 30.82 71.85 58.06 73.87 60.45 58.58 DETA conversion, % 18.34 27.46 13.91 37.28 30.93 39.64 31.46 29.46 Acyclic(N4), wt. % 97.34 96.08 96.64 92.17 95.29 92.60 95.51 95.90 Acyclic(N5), wt. % 92.34 89.17 90.46 83.69 87.90 88.50 96.63 93.47 .SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.46 0.67 0.42 0.91 0.76 0.91 0.67 0.67 Acyclic(N4)/cyclic (< = N4), 8.64 6.48 7.62 3.95 5.42 3.91 5.61 5.72 weight ratio__________________________________________________________________________ TABLE LXXIV__________________________________________________________________________ Example No. 716 717 718 719 720 721 722 723 724Catalyst Type DDDD DDDD DDDD DDDD DDDD DDDD DDDD DDDD DDDD__________________________________________________________________________Catalyst weight, gm 75 75 75 75 75 75 75 75 75Pressure, psig 607.5 600 600 600 600 600 600 600 600Temperature, .degree.C. 267.9 267.8 277.8 259.9 270.1 259.9 280.1 269.6 269Time on organics, hrs. 5 7.5 26 31.5 50 55.5 74 78 80Duration of run, hrs. 1 1 2 2 2 2 2 2 1.5MEA SV, g mol/hr/kg cat 8.48 8.57 4.17 3.96 3.90 4.22 4.15 4.01 3.97DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.673 0.822 1.742 0.612 1.367 0.688 2.430 1.370 1.341MEA 33.641 24.246 13.234 26.804 16.396 24.443 8.046 15.672 15.462PIP 0.585 1.113 0.000 0.823 1.584 0.886 1.994 1.506 1.484DETA 51.838 49.325 40.936 52.117 49.168 51.098 40.046 47.408 47.941AEEA 2.205 0.926 0.312 1.512 0.754 1.506 0.202 0.925 0.850AEP 0.502 0.953 1.969 0.613 1.431 0.666 2.287 1.330 1.326HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.488 2.104 2.220 1.660 2.270 1.751 2.342 2.219 2.195l-TETA 4.586 9.252 11.293 7.569 10.817 7.792 12.031 10.555 10.356DAEP 0.000 0.167 0.922 0.114 0.307 0.112 1.101 0.290 0.271PEEDA 0.000 0.113 0.678 0.000 0.217 0.075 0.791 0.209 0.196DPE 0.000 0.000 0.205 0.000 0.000 0.000 0.096 0.000 0.000AE-TAEA 0.234 1.259 3.575 0.885 2.431 1.011 3.561 2.057 2.019l-TEPA 0.541 2.471 6.977 1.667 5.274 1.895 7.683 4.176 3.991AE-DAEP 0.000 0.000 0.676 0.000 0.134 0.000 0.783 0.149 0.124AE-PEEDA 0.000 0.000 0.710 0.000 0.089 0.000 0.718 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.882 0.000 0.270 0.091 1.072 0.423 0.395BPEA 0.000 0.000 0.729 0.000 0.340 0.077 0.874 0.385 0.362Others 0.455 0.399 3.890 0.125 1.112 0.488 5.301 1.685 1.506MEA conversion, % 6.59 32.47 63.69 25.82 54.29 31.29 78.37 56.01 56.32DETA conversion, % 14.45 18.36 33.25 14.28 23.51 14.64 36.03 20.92 19.52Acyclic(N4), wt. % 100.00 97.59 88.22 98.78 96.15 98.08 87.85 96.23 96.41Acyclic(N5), wt. % 100.00 100.00 77.88 100.00 90.24 94.53 76.53 86.69 87.22.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.15 0.32 0.88 0.27 0.63 0.32 0.90 0.54 0.53Acyclic(N4)/cyclic (< = N4), 4.67 4.84 3.58 5.96 3.70 5.49 2.29 3.83 3.83weight ratio__________________________________________________________________________ TABLE LXXV__________________________________________________________________________ Example No. 725 726 727 728 729 730 731 732 733 734 735Catalyst Type EEEE EEEE EEEE EEEE EEEE EEEE EEEE EEEE EEEE EEEE EEEE__________________________________________________________________________Catalyst weight, gm 68.38 68.38 68.38 68.38 68.38 68.38 68.38 68.38 68.38 68.38 68.38Pressure, psig 602 602 602 602 602 603 603 602 602 602 602Temperature, .degree.C. 270 270 280 259 269 259 280 280 270.1 270 280Time on organics, hrs. 4.5 23.5 28.5 47.5 51.5 71.5 76.5 100.5 120 167.5 172.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2 2MEA SV, g mol/hr/kg cat 3.96 3.87 4.09 3.96 3.90 3.87 3.92 3.90 4.03 3.92 3.98DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.223 0.361 0.675 0.212 0.396 0.180 0.730 0.795 0.461 0.516 0.878MEA 24.445 22.069 16.449 26.779 21.362 24.727 13.740 14.037 20.260 18.745 12.739PIP 0.470 0.526 0.892 0.297 0.553 0.298 0.888 0.897 0.585 0.611 0.931DETA 53.878 51.806 46.950 56.278 50.889 55.710 44.046 42.839 49.907 47.493 41.921AEEA 2.281 2.479 1.818 2.578 2.565 2.914 1.871 1.449 2.318 2.331 1.424AEP 0.515 0.624 1.064 0.387 0.663 0.447 1.193 1.137 0.672 0.691 1.141HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.420 1.640 2.118 1.210 1.747 1.411 2.465 2.237 1.931 2.040 2.361l-TETA 7.238 7.768 10.879 5.638 8.217 6.704 12.235 11.091 9.032 9.416 11.410DAEP 0.092 0.160 0.324 0.058 0.188 0.079 0.480 0.476 0.204 0.223 0.454PEEDA 0.097 0.137 0.289 0.053 0.154 0.073 0.398 0.393 0.166 0.181 0.371DPE 0.075 0.095 0.046 0.052 0.063 0.100 0.355 0.333 0.191 0.211 0.323AE-TAEA 1.219 1.522 2.583 0.752 1.679 0.945 3.598 3.115 2.003 2.229 3.445l-TEPA 2.039 2.628 5.427 1.366 3.512 1.934 6.530 6.472 4.096 4.517 6.679AE-DAEP 0.173 0.187 0.318 0.000 0.179 0.087 0.390 0.491 0.208 0.250 0.419AE-PEEDA 0.066 0.063 0.068 0.000 0.071 0.080 0.096 0.129 0.079 0.091 0.113iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.141 0.121 0.160 0.073 0.175 0.115 0.175 0.301 0.139 0.100 0.642BPEA 0.101 0.141 0.381 0.047 0.197 0.060 0.186 0.732 0.292 0.316 0.649Others 2.821 3.594 4.790 1.260 3.582 1.974 6.576 7.895 3.856 4.550 5.879MEA conversion, % 34.76 40.66 56.27 27.73 42.89 34.28 64.11 62.93 46.18 49.40 65.33DETA conversion, % 14.55 17.21 25.83 9.80 19.14 12.00 31.61 32.77 21.21 23.81 32.19Acyclic(N4), wt. % 97.05 96.00 95.18 97.67 96.10 96.98 92.27 91.72 95.13 94.90 92.30Acyclic(N5), wt. % 87.14 89.01 89.63 94.66 89.31 89.37 92.28 85.30 89.48 89.91 84.74.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.42 0.48 0.65 0.32 0.56 0.38 0.69 0.77 0.59 0.62 0.80Acyclic(N4)/cyclic (< = N4), 7.31 6.11 4.97 8.08 6.15 8.14 4.44 4.12 6.03 5.98 4.28weight ratio__________________________________________________________________________ Example No. 736 737 738 739 740 741 742 743 Catalyst Type EEEE EEEE EEEE EEEE EEEE EEEE EEEE EEEE__________________________________________________________________________ Catalyst weight, gm 68.38 68.38 68.38 68.38 68.38 68.38 68.38 68.38 Pressure, psig 603 602 603 603 602 603 603 603 Temperature, .degree.C. 259 269 260 280 270 280 270 270 Time on organics, hrs. 191.5 196.5 214.5 219.5 238.5 243.5 262.5 266 Duration of run, hrs. 2 2 2 2 2 2 2 2 MEA SV, g mol/hr/kg cat 4.05 4.06 3.59 4.00 3.95 4.40 3.76 3.89 DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 Crude product composition, wt. % EDA 0.251 0.489 0.337 0.945 0.600 1.593 0.706 0.676 MEA 24.769 19.980 21.647 14.371 19.473 6.716 18.311 19.235 PIP 0.340 0.589 0.483 0.985 0.679 1.480 0.743 0.731 DETA 53.539 49.348 49.438 44.879 48.790 36.170 47.421 48.217 AEEA 2.555 2.352 2.505 1.539 2.260 0.475 2.170 2.155 AEP 0.402 0.686 0.479 1.175 0.770 1.905 0.803 0.752 HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 TAEA 1.480 1.962 2.037 2.311 2.070 2.556 2.174 1.990 l-TETA 6.735 8.956 8.928 10.980 9.466 13.448 10.036 9.225 DAEP 0.082 0.179 0.113 0.411 0.216 0.992 0.260 0.214 PEEDA 0.072 0.153 0.087 0.337 0.181 0.685 0.205 0.176 DPE 0.103 0.188 0.090 0.336 0.229 0.084 0.151 0.130 AE-TAEA 1.148 1.988 1.704 3.208 2.190 4.698 2.609 2.255 l-TEPA 2.110 3.632 3.226 6.048 4.274 8.949 4.512 4.130 AE-DAEP 0.072 0.068 0.065 0.302 0.149 0.729 0.156 0.129 AE-PEEDA 0.055 0.000 0.051 0.055 0.000 0.083 0.027 0.026 iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 AE-DPE 0.059 0.074 0.169 0.596 0.296 0.104 0.073 0.070 BPEA 0.081 0.221 0.152 0.558 0.257 0.781 0.053 0.056 Others 1.898 3.066 1.779 4.582 3.140 7.552 4.192 3.803 MEA conversion, % 32.69 45.43 40.15 61.44 47.63 81.50 50.64 47.61 DETA conversion, % 13.53 19.90 18.77 28.43 22.01 40.80 24.03 21.95 Acyclic(N4), wt. % 96.97 95.46 97.43 92.46 94.85 90.08 95.20 95.57 Acyclic(N5), wt. % 92.45 93.93 91.87 85.96 90.20 88.94 95.85 95.78 .SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.42 0.52 0.48 0.75 0.59 0.86 0.58 0.57 Acyclic(N4)/cyclic (< = N4), 8.23 6.09 8.76 4.10 5.56 3.11 5.65 5.60 weight ratio__________________________________________________________________________ TABLE LXXVI__________________________________________________________________________ Example No. 744 745 746 747 748 749 750 751 752 753 754Catalyst Type FFFF FFFF FFFF FFFF FFFF FFFF FFFF FFFF FFFF FFFF FFFF__________________________________________________________________________Catalyst weight, gm 68 68 68 68 68 68 68 68 68 68 68Pressure, psig 606 599 602 606 593 593 601 600 600 596 598Temperature, .degree.C. 270 270 280 260 270 260 280 280 270 271 282Time on organics, hrs. 7 26 30.5 50 55 74 79 98.8 123 158 163Duration of run, hrs. 2 2 1 2 2 2 2 2 2 2 2MEA SV, g mol/hr/kg cat 3.97 3.90 3.93 3.98 3.96 3.94 3.97 3.93 3.85 3.92 3.89DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.750 0.869 1.269 0.502 0.696 1.589 1.188 1.273 0.810 1.086 1.518MEA 14.139 13.058 7.841 19.884 13.962 19.078 8.661 6.995 13.582 13.203 6.960PIP 0.946 1.041 1.264 0.614 0.883 0.667 1.206 1.218 0.953 1.186 1.446DETA 42.338 40.333 34.679 47.727 41.491 46.874 37.218 33.635 40.430 40.181 35.494AEEA 1.641 1.480 0.679 2.213 1.609 2.241 0.609 0.617 1.541 1.261 0.505AEP 0.987 1.041 1.527 0.599 0.913 0.603 1.467 1.500 0.961 1.136 1.798HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.657 2.786 2.699 2.233 2.513 2.246 2.703 2.625 2.555 2.661 2.671l-TETA 12.825 13.469 13.932 10.488 12.891 10.468 13.856 13.911 12.446 13.232 14.206DAEP 0.340 0.387 0.763 0.170 0.305 0.165 0.693 0.770 0.335 0.452 0.939PEEDA 0.302 0.336 0.601 0.150 0.277 0.146 0.549 0.605 0.284 0.372 0.692DPE 0.132 0.150 0.301 0.094 0.099 0.099 0.088 0.118 0.077 0.076 0.107AE-TAEA 3.574 3.998 4.830 2.253 3.538 2.309 4.432 4.606 3.500 4.013 4.667l-TEPA 7.216 7.943 9.991 4.612 7.184 4.724 9.147 9.831 7.304 8.152 9.680AE-DAEP 0.088 0.082 0.204 0.154 0.134 0.064 0.601 0.879 0.328 0.401 0.783AE-PEEDA 0.155 0.158 0.380 0.028 0.223 0.074 0.067 0.125 0.039 0.047 0.080iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.038 0.067 0.403 0.056 0.248 0.075 0.078 0.313 0.048 0.057 0.105BPEA 0.508 0.179 1.040 0.229 0.611 0.231 0.804 0.839 0.472 0.607 0.902Others 5.025 5.875 9.178 2.946 5.812 3.348 7.734 8.939 4.826 5.537 8.116MEA conversion, % 62.09 64.96 79.02 46.40 62.51 48.13 76.57 80.72 62.33 64.77 81.20DETA conversion, % 32.54 35.67 44.85 23.54 33.79 24.26 40.15 44.90 33.36 36.28 43.03Acyclic(N4), wt. % 95.24 94.91 90.90 96.85 95.77 96.87 92.56 91.71 95.57 94.64 90.67Acyclic(N5), wt. % 93.19 96.09 87.98 93.64 89.81 94.07 89.76 87.00 92.42 91.63 88.47.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.71 0.73 0.92 0.56 0.74 0.57 0.85 0.92 0.74 0.79 0.87Acyclic(N4)/cyclic (< = N4), 5.72 5.50 3.73 7.82 6.22 7.57 4.14 3.93 5.75 4.93 3.39weight ratio__________________________________________________________________________ Example No. 755 756 757 758 759 760 761 762 763 764 765Catalyst Type FFFF FFFF FFFF FFFF FFFF FFFF FFFF FFFF FFFF FFFF FFFF__________________________________________________________________________Catalyst weight, gm 68 68 68 68 68 68 68 68 67.2 67.2 67.2Pressure, psig 602 603 602 602 603 603 603 603 600 600 600Temperature, .degree.C. 260 270 260 281 272 280 272 271 267.7 267.9 278Time on organics, hrs. 182 187 206 211 272 235 254 257.5 4 6.5 28.5Duration of run, hrs. 2 2 83.7 2 2 2 2 2 2 2 2MEA SV, g mol/hr/kg cat 3.99 3.83 0.09 3.85 3.80 3.88 3.86 4.03 4.59 4.81 4.66DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.564 0.960 0.630 1.769 1.921 2.220 1.641 1.650 0.515 0.541 1.593MEA 18.056 12.558 17.829 6.838 12.002 5.827 11.663 13.072 23.588 25.727 18.012PIP 0.765 1.101 0.770 1.362 1.263 1.380 1.178 1.205 0.888 1.118 1.953DETA 45.781 40.874 44.267 34.368 39.115 30.652 38.907 40.441 54.811 54.100 50.845AEEA 2.117 1.385 2.108 0.517 1.158 0.441 1.197 1.308 0.344 0.802 0.233AEP 0.738 1.161 0.699 1.725 1.205 1.595 1.179 1.119 0.883 0.858 1.884HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.384 2.732 2.320 2.531 2.548 2.402 2.575 2.513 1.618 1.490 1.878l-TETA 11.386 13.549 11.117 13.437 12.752 13.162 12.893 12.524 7.964 7.269 9.198DAEP 0.225 0.438 0.196 0.889 0.485 0.981 0.469 0.410 0.114 0.093 0.645PEEDA 0.187 0.361 0.175 0.670 0.383 0.728 0.375 0.335 0.081 0.064 0.387DPE 0.056 0.091 0.033 0.111 0.077 0.133 0.082 0.076 0.000 0.000 0.000AE-TAEA 2.669 3.990 2.705 4.603 4.023 4.890 3.878 3.770 0.000 0.088 0.246l-TEPA 5.588 8.225 5.696 9.840 8.145 10.433 8.054 7.706 0.664 0.704 1.555AE-DAEP 0.156 0.382 0.201 0.171 0.377 0.235 0.379 0.324 0.000 0.223 0.372AE-PEEDA 0.028 0.051 0.028 0.114 0.042 0.161 0.048 0.037 0.000 0.000 0.099iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.046 0.043 0.036 0.053 0.049 0.706 0.047 0.046 0.168 0.000 0.059BPEA 0.324 0.630 0.311 0.897 0.644 1.020 0.619 0.582 0.000 0.000 0.000Others 3.310 5.711 3.339 10.005 5.502 13.484 5.564 5.184 1.532 0.963 2.990MEA conversion, % 51.33 66.74 50.94 81.35 67.32 84.30 67.93 64.52 34.18 28.60 49.97DETA conversion, % 26.65 35.67 27.60 44.30 36.70 50.93 36.43 34.77 9.11 10.77 16.06Acyclic(N4), wt. % 96.72 94.81 97.08 90.53 94.19 89.41 94.35 94.83 98.01 98.23 91.48Acyclic(N5), wt. % 93.71 91.70 93.58 92.12 91.63 87.84 91.61 92.07 79.79 78.07 77.26.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.62 0.78 0.65 0.89 0.82 1.00 0.79 0.79 0.09 0.11 0.19Acyclic(N4)/cyclic (< = N4), 6.99 5.16 7.17 3.36 4.48 3.23 4.71 4.78 4.87 4.11 2.27weight ratio__________________________________________________________________________ Example No. 766 767 768 769 770 771 Catalyst Type FFFF FFFF FFFF FFFF FFFF FFFF__________________________________________________________________________ Catalyst weight, gm 67.2 67.2 67.2 67.2 67.2 67.2 Pressure, psig 600 600 600 600 600 600 Temperature, .degree.C. 257.8 269.6 259.3 279.3 269.8 270.1 Time on organics, hrs. 47.5 52.5 71 76.5 96.5 99 Duration of run, hrs. 2 2 2 2 2 2 MEA SV, g mol/hr/kg cat 4.74 4.80 4.79 4.46 4.63 4.60 DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 Crude product composition, wt. % EDA 0.567 0.832 0.445 1.675 0.932 0.995 MEA 26.580 21.992 27.189 13.854 20.859 20.291 PIP 1.009 1.390 0.957 1.810 1.493 1.486 DETA 55.433 53.042 56.685 51.796 53.039 51.623 AEEA 0.360 0.208 0.377 0.150 0.478 0.210 AEP 0.856 1.352 0.775 2.177 1.423 1.423 HEP 0.000 0.000 0.000 0.000 0.000 0.000 TAEA 1.474 1.695 1.397 1.977 1.858 1.955 l-TETA 6.586 8.327 6.490 9.962 8.880 10.270 DAEP 0.301 0.154 0.207 0.692 0.412 0.178 PEEDA 0.144 0.104 0.117 0.359 0.162 0.125 DPE 0.000 0.000 0.000 0.000 0.000 0.000 AE-TAEA 0.000 0.102 0.000 1.894 0.109 0.000 l-TEPA 0.500 0.975 0.246 3.556 1.157 1.321 AE-DAEP 0.000 0.000 0.000 0.114 0.133 0.326 AE-PEEDA 0.000 0.175 0.000 0.075 0.000 0.069 iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 AE-DPE 0.000 0.423 0.000 0.000 0.083 0.512 BPEA 0.000 0.000 0.000 0.000 0.000 0.000 Others 1.492 2.047 0.994 0.880 1.861 2.579 MEA conversion, % 27.10 38.81 25.75 61.46 42.13 44.20 DETA conversion, % 9.64 12.29 7.99 14.37 12.55 15.64 Acyclic(N4), wt. % 94.77 97.49 96.05 91.91 94.93 97.59 Acyclic(N5), wt. % 100.00 64.30 100.00 96.64 85.40 59.30 .SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.06 0.16 0.03 0.43 0.13 0.18 Acyclic(N4)/cyclic (< = N4), 3.49 3.34 3.83 2.37 3.08 3.81 weight ratio__________________________________________________________________________ TABLE LXXVII__________________________________________________________________________ Example No. 772 773 774 775 776 777 778Catalyst Type GGGG GGGG GGGG GGGG GGGG GGGG GGGG__________________________________________________________________________Catalyst weight, gm 69.34 69.34 69.34 69.34 69.34 69.34 69.34Pressure, psig 604 603 603 604 604 603 603Temperature, .degree.C. 270 270 280 260 270 260 280Time on organics, hrs. 7 26 30.5 50 55 74 79Duration of run, hrs. 2 2 1 2 2 2 2MEA SV, g mol/hr/kg cat 4.33 4.26 4.21 4.20 4.33 4.20 4.17DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.805 1.034 1.662 0.510 0.908 0.544 1.363MEA 14.316 13.747 10.093 20.646 15.418 19.410 8.991PIP 0.832 0.927 1.260 0.542 0.841 0.555 1.085DETA 41.647 40.641 36.709 48.819 43.537 47.902 35.150AEEA 1.392 1.332 0.661 2.056 1.526 2.142 0.718AEP 0.990 1.057 1.455 0.554 0.915 0.588 1.336HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.980 2.906 2.683 2.272 2.709 2.329 2.593l-TETA 13.276 13.074 12.859 9.750 12.028 10.013 12.850DAEP 0.416 0.470 0.726 0.152 0.358 0.171 0.754PEEDA 0.321 0.347 0.527 0.130 0.270 0.147 0.531DPE 0.151 0.167 0.208 0.055 0.159 0.073 0.126AE-TAEA 4.148 4.074 4.997 2.219 3.441 2.254 4.357l-TEPA 7.057 7.074 8.378 3.718 6.209 3.871 8.283AE-DAEP 0.081 0.074 0.124 0.145 0.075 0.247 1.053AE-PEEDA 0.148 0.141 0.238 0.027 0.117 0.067 0.154iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.051 0.069 0.286 0.266 0.175 0.261 0.309BPEA 0.582 0.570 0.800 0.207 0.479 0.205 0.737Others 5.099 5.415 7.215 2.423 4.615 2.781 8.931MEA conversion, % 61.90 63.00 72.52 43.91 58.54 46.90 75.19DETA conversion, % 34.13 35.00 40.60 21.18 30.42 22.12 42.36Acyclic(N4), wt. % 94.82 94.20 91.41 97.28 94.93 96.93 91.63Acyclic(N5), wt. % 92.86 92.88 90.23 90.21 91.94 88.71 84.88.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.70 0.71 0.87 0.53 0.68 0.54 0.88Acyclic(N4)/cyclic (< = N4), 6.00 5.38 3.72 8.39 5.80 8.05 4.03weight ratio__________________________________________________________________________ Example No. 779 780 781 782 783 784 785Catalyst Type GGGG GGGG GGGG GGGG GGGG GGGG GGGG__________________________________________________________________________Catalyst weight, gm 69.34 69.34 69.34 69.34 69.34 69.34 69.34Pressure, psig 600 600 603 604 603 604 603Temperature, .degree.C. 280 270 271 282 260 270 260Time on organics, hrs. 98.8 123 158 163 182 187 206Duration of run, hrs. 2 2 2 2 2 2 2MEA SV, g mol/hr/kg cat 4.26 4.16 4.01 4.31 4.28 4.05 4.11DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 2.077 0.963 1.212 1.778 0.757 0.980 0.861MEA 9.550 15.047 12.554 9.298 20.034 13.105 18.882PIP 1.325 0.906 1.009 1.387 0.734 0.962 0.794DETA 32.997 41.105 37.117 36.552 46.016 38.892 44.565AEEA 0.580 1.445 1.046 0.554 1.888 1.280 1.745AEP 1.810 0.927 1.212 1.598 0.679 0.976 0.784HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.994 2.443 2.311 2.549 2.223 2.513 2.187l-TETA 10.946 11.547 11.703 13.076 10.211 11.973 10.178DAEP 1.270 0.373 0.669 0.839 0.209 0.394 0.335PEEDA 0.858 0.292 0.476 0.594 0.174 0.318 0.240DPE 0.164 0.196 0.112 0.468 0.072 0.186 0.150AE-TAEA 3.447 3.193 3.397 4.484 2.580 3.922 2.727l-TEPA 7.231 6.092 7.003 8.450 5.015 7.390 5.407AE-DAEP 1.912 0.489 0.928 0.694 0.198 0.427 0.351AE-PEEDA 0.294 0.065 0.153 0.085 0.045 0.079 0.059iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.130 0.070 0.287 0.093 0.051 0.166 0.042BPEA 0.613 0.415 0.510 0.761 0.054 0.563 0.330Others 12.620 4.609 7.302 7.358 3.390 6.493 3.912MEA conversion, % 73.83 57.94 64.82 74.69 45.65 63.83 48.59DETA conversion, % 46.26 31.71 38.19 40.86 25.81 36.20 27.88Acyclic(N4), wt. % 84.95 94.20 91.77 89.15 96.47 94.16 94.46Acyclic(N5), wt. % 78.36 89.93 84.70 88.79 95.62 90.16 91.23.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.89 0.70 0.80 0.83 0.62 0.82 0.68Acyclic(N4)/cyclic (< = N4), 2.38 5.19 4.03 3.20 6.65 5.11 5.37weight ratio__________________________________________________________________________ Example No. 786 787 788 789 790 Catalyst Type GGGG GGGG GGGG GGGG GGGG__________________________________________________________________________ Catalyst weight, gm 69.34 69.34 69.34 69.34 69.34 Pressure, psig 604 604 604 603 604 Temperature, .degree.C. 281 272 280 272 271 Time on organics, hrs. 211 272 235 254 257.5 Duration of run, hrs. 2 2 2 2 2 MEA SV, g mol/hr/kg cat 4.41 4.13 4.11 4.22 4.43 DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 Crude product composition, wt. % EDA 2.156 1.946 2.350 1.794 1.594 MEA 8.720 12.941 7.170 13.118 13.362 PIP 1.385 1.150 1.343 1.147 1.045 DETA 34.824 39.610 33.663 39.912 39.851 AEEA 0.521 1.185 0.478 1.195 1.279 AEP 1.518 1.109 1.669 1.094 1.015 HEP 0.000 0.000 0.000 0.000 0.000 TAEA 2.296 2.546 2.452 2.458 2.496 l-TETA 12.160 12.466 13.106 12.081 12.149 DAEP 0.916 0.518 1.012 0.454 0.423 PEEDA 0.634 0.377 0.766 0.348 0.321 DPE 0.127 0.092 0.123 0.079 0.072 AE-TAEA 4.290 3.863 4.417 3.624 3.540 l-TEPA 8.840 7.583 9.218 7.097 6.990 AE-DAEP 0.189 0.411 0.892 0.342 0.038 AE-PEEDA 0.132 0.052 0.135 0.036 0.038 iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 AE-DPE 0.411 0.073 0.390 0.091 0.061 BPEA 0.822 0.597 0.843 0.577 0.535 Others 10.339 5.881 9.704 5.473 5.321 MEA conversion, % 76.20 64.94 80.41 63.82 62.91 DETA conversion, % 43.50 36.22 45.35 34.58 34.25 Acyclic(N4), wt. % 89.61 93.83 89.12 94.28 94.72 Acyclic(N5), wt. % 89.42 91.00 85.78 91.11 91.63 .SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.91 0.79 0.91 0.76 0.74 Acyclic(N4)/cyclic (< = N4), 3.16 4.63 3.17 4.66 5.09 weight ratio__________________________________________________________________________ TABLE LXXVIII__________________________________________________________________________ Example No. 791 792 793 794 795 796 797 798 799Catalyst Type HHHH HHHH HHHH HHHH HHHH HHHH HHHH HHHH HHHH__________________________________________________________________________Catalyst weight, gm 70.6 70.6 70.6 70.6 70.6 70.6 70.6 70.6 70.6Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 267.7 267.9 278 257.8 269.6 259.3 279.3 269.8 270.1Time on organics, hrs. 4 6.5 30.5 49.5 54.5 73 78.5 98 101Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, g mol/hr/kg cat 4.23 4.29 4.10 4.04 4.14 4.15 3.89 3.94 3.95DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.162 0.169 0.783 0.192 0.397 0.176 1.073 0.529 0.553MEA 29.144 31.908 24.483 32.053 27.952 31.487 22.456 25.861 26.009PIP 0.349 0.340 1.209 0.251 0.651 0.248 1.406 0.768 0.760DETA 59.742 58.534 56.565 58.955 59.279 59.506 54.811 57.648 57.364AEEA 0.310 0.929 0.200 0.321 0.342 0.351 0.776 0.366 0.370AEP 0.544 0.498 1.287 0.436 0.711 0.471 1.454 0.793 0.801HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.578 0.706 0.873 0.618 0.733 0.669 1.573 0.874 1.310l-TETA 4.153 2.968 6.200 2.623 4.926 2.835 6.907 5.628 5.841DAEP 0.177 0.175 0.342 0.144 0.238 0.180 0.520 0.239 0.184PEEDA 0.076 0.000 0.220 0.000 0.135 0.000 0.347 0.085 0.125DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.060 0.000 0.000AE-TAEA 0.000 0.000 0.000 0.000 0.000 0.000 0.236 0.000 0.000l-TEPA 0.000 0.000 0.463 0.000 0.000 0.000 0.848 0.318 0.401AE-DAEP 0.000 0.000 0.000 0.000 0.000 0.000 0.181 0.000 0.000AE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.279 0.000 0.000BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 0.976 0.215 1.483 1.078 1.416 1.247 1.734 1.491 2.212MEA conversion, % 20.13 12.23 32.26 12.02 24.15 14.16 38.70 28.47 29.14DETA conversion, % 2.69 4.31 6.99 3.83 4.40 3.59 11.07 5.24 7.12Acyclic(N4), wt. % 94.94 95.46 92.64 95.76 93.82 95.11 90.14 95.25 95.85Acyclic(N5), wt. % -- -- 100.00 -- -- -- 70.20 100.00 100.00.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.00 0.00 0.00 0.00 0.00 0.00 0.16 0.05 0.05Acyclic(N4)/cyclic (< = N4), 4.13 3.63 2.31 3.90 3.26 3.90 2.24 3.45 3.82weight ratio__________________________________________________________________________ TABLE LXXIX__________________________________________________________________________ Example No. 800 801 802 803 804 805 806 807 808 809 810Catalyst Type IIII IIII IIII IIII IIII IIII IIII IIII IIII IIII IIII__________________________________________________________________________Catalyst weight, gm 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5Pressure, psig 598 597 597 598 598 598 598 600 600 585 598Temperature, .degree.C. 270 270 280 260 270 260 280 280 270 271 282Time on organics, hrs. 7 26 30.5 50 55 74 79 98.8 123 158 163Duration of run, hrs. 2 2 1 2 2 2 2 2 2 2 2MEA SV, g mol/hr/kg cat 3.62 3.73 3.53 3.46 3.70 3.56 3.47 3.46 3.40 2.97 3.69DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97Crude product composition, wt. %EDA 0.294 0.424 0.706 0.273 0.506 0.342 0.979 1.001 0.624 0.764 1.129MEA 25.314 22.475 18.589 26.092 22.747 25.743 18.317 16.142 21.635 20.571 16.885PIP 0.421 0.496 0.707 0.266 0.485 0.297 0.712 0.692 0.469 0.531 0.826DETA 54.036 51.203 48.723 54.115 53.329 54.167 48.580 42.653 47.745 47.941 46.768AEEA 1.899 2.033 1.670 2.115 2.193 2.258 1.799 1.403 1.963 1.707 1.530AEP 0.488 0.616 0.869 0.374 0.614 0.438 0.855 0.848 0.588 0.697 1.034HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.340 1.728 1.888 1.215 1.590 1.290 1.768 1.764 1.551 1.641 1.964l-TETA 6.203 8.239 9.101 5.680 7.515 6.023 8.740 9.202 7.737 8.006 9.717DAEP 0.091 0.205 0.282 0.096 0.157 0.110 0.267 0.415 0.216 0.239 0.408PEEDA 0.093 0.162 0.229 0.076 0.133 0.090 0.209 0.313 0.172 0.186 0.297DPE 0.048 0.111 0.178 0.076 0.126 0.084 0.220 0.387 0.232 0.211 0.069AE-TAEA 1.230 1.884 2.347 1.338 1.704 1.006 1.902 2.806 1.832 1.858 2.661l-TEPA 2.363 3.385 4.197 1.841 2.798 1.882 3.504 5.099 3.159 3.247 5.154AE-DAEP 0.139 0.145 0.257 0.143 0.273 0.114 0.392 0.812 0.539 0.401 0.342AE-PEEDA 0.066 0.034 0.101 0.042 0.061 0.024 0.100 0.168 0.078 0.057 0.062iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.043 0.117 0.077 0.157 0.090 0.062 0.343 0.035 0.053 0.067BPEA 0.110 0.211 0.290 0.056 0.110 0.069 0.063 0.209 0.048 0.051 0.390Others 2.415 3.286 4.610 2.509 3.660 2.432 4.633 8.202 4.835 4.459 5.997MEA conversion, % 31.77 40.08 50.03 29.37 39.57 30.42 49.72 55.92 40.42 42.93 55.07DETA conversion, % 13.44 18.87 22.15 12.94 17.39 12.99 20.75 30.77 21.85 20.95 26.04Acyclic(N4), wt. % 97.01 95.43 94.10 96.54 95.63 96.27 93.80 90.77 93.73 93.81 93.79Acyclic(N5), wt. % 91.93 92.41 89.53 90.91 88.22 90.67 89.75 83.77 87.68 90.08 90.08.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.50 0.55 0.63 0.49 0.54 0.42 0.54 0.78 0.57 0.55 0.70Acyclic(N4)/cyclic (< = N4), 6.61 6.27 4.85 7.78 6.01 7.18 4.65 4.13 5.53 5.17 4.43weight ratio__________________________________________________________________________ Example No. 811 812 813 814 815 816 817 818 Catalyst Type IIII IIII IIII IIII IIII IIII IIII IIII__________________________________________________________________________ Catalyst weight, gm 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 Pressure, psig 598 598 598 598 598 598 598 598 Temperature, .degree.C. 260 270 260 281 272 280 272 271 Time on organics, hrs. 182 187 206 211 272 235 254 257.5 Duration of run, hrs. 2 2 2 2 2 2 2 2 MEA SV, g mol/hr/kg cat 3.58 3.41 3.41 3.54 3.99 3.53 3.50 3.70 DETA/MEA mole ratio 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 NH.sub.3 /MEA mole ratio 5.97 5.97 5.97 5.97 5.97 5.97 5.97 5.97 Crude product composition, wt. % EDA 0.479 0.786 0.509 1.756 1.803 1.993 1.749 1.597 MEA 25.262 21.504 25.342 18.397 20.631 15.100 20.996 22.350 PIP 0.351 0.538 0.352 0.865 0.634 0.781 0.638 0.567 DETA 52.656 48.687 51.138 47.357 46.647 42.162 46.440 48.370 AEEA 2.132 1.979 2.129 1.620 1.738 1.446 1.730 1.824 AEP 0.470 0.636 0.432 0.927 0.707 0.935 0.676 0.626 HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 TAEA 1.408 1.541 1.337 1.743 1.648 1.942 1.596 1.530 l-TETA 6.641 7.305 6.278 8.432 8.037 9.595 7.922 7.422 DAEP 0.135 0.174 0.125 0.291 0.359 0.442 0.295 0.232 PEEDA 0.101 0.138 0.094 0.224 0.234 0.314 0.215 0.169 DPE 0.110 0.183 0.114 0.089 0.099 0.103 0.182 0.107 AE-TAEA 1.266 1.659 1.462 2.013 2.165 2.975 2.063 1.905 l-TEPA 2.314 2.935 2.396 3.688 3.984 5.395 3.860 3.394 AE-DAEP 0.130 0.223 0.173 0.261 0.335 0.507 0.256 0.234 AE-PEEDA 0.025 0.068 0.063 0.045 0.076 0.117 0.056 0.042 iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 AE-DPE 0.086 0.211 0.083 0.034 0.229 0.080 0.055 0.040 BPEA 0.040 0.087 0.037 0.225 0.294 0.465 0.272 0.231 Others 2.874 5.176 3.565 5.035 6.180 8.307 5.107 4.381 MEA conversion, % 31.89 40.98 31.07 49.41 44.79 58.84 42.66 32.29 DETA conversion, % 15.63 20.58 17.33 22.60 25.81 31.71 24.63 31.91 Acyclic(N4), wt. % 95.88 94.70 95.80 94.40 93.33 93.06 93.21 94.64 Acyclic(N5), wt. % 92.72 88.64 91.56 90.98 86.82 87.74 90.25 90.67 .SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.46 0.55 0.53 0.58 0.68 0.77 0.64 0.62 Acyclic(N4)/cyclic (< = N4), 6.90 5.30 6.82 4.25 4.76 4.48 4.47 5.26 weight ratio__________________________________________________________________________

Although the invention has been illustrated by certain of the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.

Claims

1. A process of making polyalkylene polyamines which comprises condensing an amino compound comprising at least one of ammonia and one or more organic compounds containing nitrogen to which is bonded an active hydrogen, with a high surface area Group IVB metal oxide condensation catalyst selected from the group consisting of hafnium oxide having a surface area greater than about 70 m.sup.2 /gm, zirconium oxide having a surface area greater than about 70 m.sup.2 /gm, titanium oxide having a surface area greater than about 140 m.sup.2 /gm and mixtures thereof.

2. The process of claim 1 wherein the titanium oxide condensation catalyst comprises titanium dioxide.

3. The process of claim 1 wherein the zirconium oxide condensation catalyst comprises zirconium dioxide.

4. The process of claim 1 wherein the condensation catalyst comprises a mixture of titanium dioxide and zirconium dioxide.

5. The process of claim 1 wherein the catalyst is associated with a support material.

6. The process of claim 5 wherein the support comprises an alumina material or an alumina-silica material.

7. The process of claim 5 wherein the support comprises a silica material or a silica-alumina material.

8. The process of claim 5 wherein the support comprises from about 5 to about 50 percent by weight of the catalyst.

9. The process of claim 1 wherein the catalyst contains a performance moderator that enhances product selectivity of the process.

10. The process of claim 9 wherein the performance moderator comprises one or more metal oxides.

11. The process of claim 11 wherein the performance moderator comprises one or more Group IA metal oxides, Group IIA metal oxides, Group IIIB metal oxides, Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VIII metal oxides, Group IB metal oxides, Group IIB metal oxides, Group IIIA metal oxides, Group IVA metal oxides, Group VA metal oxides, Group VIA metal oxides, other Group IVB metal oxides or mixtures thereof.

12. The process of claim 11 wherein the performance moderator comprises one or more oxides of scandium, yttrium, lanthanum, cerium, gadolinium, lutetium, ytterbium, niobium, tantalum, chromium, molybdenum, tungsten, titanium, zirconium, iron, cobalt, nickel, zinc, cadmium, boron, aluminum, gallium, indium, silicon, germanium, tin, lead, arsenic, antimony and bismuth.

13. The process of claim 9 wherein the performance moderator comprises one or more metallic phosphates having a cyclic structure or an acylic structure, metallic polyphosphates having a condensed structure, metallic metaphosphimates, metallic phosphoramidates, metallic amidophosphates, metallic imidophosphates or mixtures thereof.

14. The process of claim 13 wherein the performance moderator comprises sodium dihydrogen phosphate, sodium trimetaphosphate, disodium dihydrogen pyrophosphate, sodium tripolyphosphate or mixtures thereof.

15. The process of claim 1 wherein the Group IVB metal oxide condensation catalyst comprises a mixed oxide of a Group IVB metal oxide and one or more other metal oxides.

16. The process of claim 15 wherein the metal oxide comprises one or more Group IA metal oxides, Group IIA metal oxides, Group IIIB metal oxides, Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VIII metal oxides, Group IB metal oxides, Group IIB metal oxides, Group IIIA metal oxides, Group IVA metal oxides, Group VA metal oxides, Group VIA metal oxides, other Group IVB metal oxides or mixtures thereof.

17. The process of claim 15 wherein the metal oxide comprises one or more oxides of scandium, yttrium, lanthanum, cerium, gadolinium, lutetium, ytterbium, niobium, tantalum, chromium, molybdenum, tungsten, titanium, zirconium, iron, cobalt, nickel, zinc, cadmium, boron, aluminum, gallium, indium, silicon, germanium, tin, lead, arsenic, antimony and bismuth.

18. The process of claim 1 wherein the Group IVB metal oxide condensation catalyst comprises a Group IVB metal oxide in an amount of from about 50 weight percent to about 100 weight percent of the weight of the catalyst.

19. The process of claim 1 wherein the Group IVB metal oxide condensation catalyst comprises a Group IVB metal oxide in an amount of from about 75 weight percent to about 100 weight percent of the weight of the catalyst.

20. The process of claim 1 wherein the Group IVB metal oxide condensation catalyst comprises a Group IVB metal oxide in an amount of from about 90 weight percent to about 100 weight percent of the weight of the catalyst.

21. The process of claim 1 wherein the amino compound comprises an alkyleneamine.

22. The process of claim 1 wherein the condensation further comprises condensing the amino compound with a compound containing an alcoholic hydroxy group.

23. The process of claim 22 wherein the amino compound is ammonia.

24. The process of claim 133 wherein the compound containing an alcoholic hydroxy group is an alkanolamine or an alkylene glycol.

25. The process of claim 24 wherein the alkanolamine is aminoethylethanolamine.

26. The process of claim 22 wherein the amino compound comprises ethylenediamine or diethylenetriamine and the compound containing the alcoholic hydroxy group is ethylene glycol.

27. The process of claim 1 wherein the amino compound comprises a mixture of monoethanolamine and ethylenediamine.

28. The process of claim 1 wherein the amino compound comprises a mixture of monoethanolamine and diethylenetriamine.

29. The process of claim 1 wherein the amino compound comprises a mixture of monoethanolamine, ethylenediamine and ammonia.

30. The process of claim 1 wherein the amino compound comprises a mixture of monoethanolamine, diethylenetriamine and ammonia.

31. The process of claim 1 wherein the amino compound comprises a mixture of aminoethylethanolamine and ethylenediamine.

32. The process of claim 1 wherein the amino compound comprises a mixture of aminoethylethanolamine and diethylenetriamine.

33. The process of claim 1 wherein the amino compound comprises a mixture of aminoethylethanolamine, ethylenediamine and ammonia.

34. The process of claim 1 wherein the amino compound comprises a mixture of aminoethylethanolamine, diethylenetriamine and ammonia.

35. The process of claim 1 wherein the amino compound comprises a mixture of diethanolamine and ethylenediamine or a mixture of diethanolamine and diethylenetriamine.

36. The process of claim 1 wherein the amino compound comprises a mixture of dihydroxyethylethylenediamine and ethylenediamine or a mixture of dihydroxyethylethylenediamine and diethylenetriamine.

37. The process of claim 1 wherein the amino compound comprises a mixture of hydroxyethyldiethylenetriamine and ethylenediamine or a mixture of hydroxyethyldiethylenetriamine and diethylenetriamine.

38. The process of claim 1 wherein the amino compound comprises a mixture of hydroxyethyltriethylenetetramine and ethylenediamine or a mixture of hydroxyethyltriethylenetetramine and diethylenetriamine.

39. The process of claim 1 which is effected in the liquid phase, vapor phase, supercritical liquid phase or mixtures thereof.

40. A process of making alkylamines which comprises condensing an alcohol and at least one of a primary amine, a secondary amine or a tertiary amine with a high surface area Group IVB metal oxide condensation catalyst.