Amines catalysis using metallic phosphate condensation catalysts having a cyclic structure

RELATED APPLICATIONS
U.S. patent application Ser. No. 136,615, filed Dec. 22, 1987, commonly-assigned.
The following are related, commonly assigned applications, filed on an even date herewith: U.S. patent application Ser. No. (390,829), U.S. patent application Ser. No. (390,709); U.S. patent application Ser. No. (390,714); U.S. patent application Ser. No. (390,828); and U.S. patent application Ser. No. (390,708); all incorporated herein by reference.
BRIEF SUMMARY OF THE INVENTION
1. Technical Field
This invention relates to a process for making amines by condensing an amino compound in the presence of a metallic phosphate condensation catalyst having a cyclic structure or an acyclic structure which is transformed into a cyclic structure during said process.
This invention also relates to an alkyleneamines producers composition rich in higher polyalkylene polyamines such as triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA).
2. Background of the Invention
There is a substantial body of literature directed to the use of various 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 enerates 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 describes 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.
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.
U.S. Pat. No. 4,683,335 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.
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.
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 Patent Applications 0 069 322, 0 111 928 and 0 158 319; East German Patent No. 206,896; Japanese Patent Publication No. 51-141895; and French Patent No. 1,381,243. The evolution of the art to the use of the acid catalyzed condensation reaction to generate acyclic alkyleneamines, particularly acyclic polyalkylenepolyamines, as the predominant products stemmed from the initial disclosure in U.S. Pat. No. 4,036,881, 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 and U.S. Pat. No. 4,463,193 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 of acidic metal phosphates, reaction. 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 phosphorus 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 of acidic metal phosphates, reaction. 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 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 liquid phase reaction.U.S. Pat. No. 4,362,886 Arsenic, antimony or bismuth Alkanolamie and an alkylene- containing compounds. Antimony amine in liquid phase sulfate specifically disclosed. reaction.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. acid.U.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 alkanol- amine.U.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 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 phosphorus 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.__________________________________________________________________________
The market demand for higher polyalkylene polyamines such as TETA, TEPA and PEHA has been progressively increasing in recent years. These higher polyalkyene polyamines are desirable co-products with DETA. It would be desirable to satisfy the existing demand from a cost standpoint by modifying slightly the commercial processes directed to the manufacture of DETA from the reaction of MEA and EDA or other suitable starting raw materials such as DETA and AEEA, to the production of TETA, TEPA and PEHA as major products.
It would be desirable to have continuously produced compositions, generated by the reaction of MEA and EDA or other suitable starting raw materials such as DETA and AEEA over a fixed bed of a condensation catalyst under commercial conditions, that are rich in TETA, TEPA and PEHA, and that are not disproporationately high in PIP and other cyclics.
It would be very beneficial to have a process which increases one's ability to generate the manufacture of desirable higher polyalkylene polyamine products such as TETA, TEPA and PEHA without generating large amounts of cyclic alkylenepolyamine products. In addition, it would also be desirable to have a process with raw material flexibility which provides the potential to control congener distribution, linear to cyclic selectivity and linear to branched selectivity of the higher polyalkylene polyamines products. As used herein, congener distribution refers to polyalkylene polyamines containing the same number of nitrogen atoms but not necessarily having the same molecular weight or structure.
The above features are provided by this invention.
SUMMARY OF THE INVENTION
This invention relates in general to a process of making amines which comprises condensing an amino compound in the presence of a metallic phosphate condensation catalyst having a cyclic structure or an acyclic structure which is transformed into a cyclic structure during said process. The metallic phosphate condensation catalysts used herein contain sufficient residual bound hydroxyl groups or other groupings which renders catalyst formation possible by loss of water or its chemical equivalent such as ammonium hydroxide.
More particularly, 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 certain metallic phosphates having a cyclic structure or an acyclic structure which is transformed into a cyclic structure during said process as the condensation catalyst. A preferred process involves the manufacture of alkyleneamines, most desirably higher polyalkylene polyamines, by such condensation reactions utilizing sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate or sodium trimetaphosphate as the condensation catalyst.
The invention further relates to a continuously generated alkyleneamines producers composition comprising, based on 100 percent of the weight of the composition and exclusive of any water and/or ammonia present,
a) greater than about 3.0 weight percent of the combination of TETA and TEPA,
b) greater than about 0.1 weight percent of TEPA,
c) greater than about 3.0 weight percent of TETA,
d) less than about 90.0 weight percent of DETA and/or EDA,
e) less than about 90.0 weight percent of MEA and/or AEEA,
f) less than about 12.5 weight percent of the combination of PIP and AEP,
g) less than about 15.0 weight percent of other polyalkylene polyamines,
h) a TETA+TAEA to PIP+AEP+PEEDA+DAEP+DPE weight ratio of greater than about 0.5,
i) a TEPA+AETAEA to PIP+AEP+PEEDA+DAEP+DPE+AEPEEDA+iAEPEEDA AEDAEP+AEDPE+BPEA weight ratio of greater than about 0.5,
j) a TETA to TAEA weight ratio of greater than about 2.0, and
k) a TEPA to AETAEA weight ratio of greater than about 2.0.
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
The higher polyalkylene polyamines 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. As indicated above, there is lacking a commercial process for the manufacture of enhanced quantities of TETA, TEPA and PEHA especially as significant products of reaction. There is thus a need for the ability to commercially generate larger production quantities of TETA, TEPA and PEHA and that is the direction of this invention. The process of this invention provides for the reaction of MEA and DETA or other suitable starting raw materials such as EDA and AEEA to produce in a continuous manner a reaction product mixture, termed herein an "alkyleneamines producers composition", in which TETA, TEPA and PEHA are principal products of the reaction.
The process of this invention is distinctive insofar as it achieves the generation of high concentrations of TETA, TEPA and PEHA in a manner which can be suitably employed in a commercial process, particularly a continuous process, for the manufacture of alkyleneamines. In particular, the process of this invention allows the production of TETA, TEPA and PEHA in relatively high yields without generating large amounts of cyclic polyalkylene polyamine products. The process of this invention provides starting raw material flexibility thereby allowing the potential to control congener distribution, linear to cyclic selectivity and linear to branched selectivity of the higher polyalkylene polyamine products.
As indicated above, this invention relates to a process of making amines which comprises condensing an amino compound in the presence of a metallic phosphate condensation catalyst having a cyclic structure or an acyclic structure which is transformed into a cyclic structure during said process.
As also indicated above, this invention relates to a continuously generated alkyleneamines producers composition comprising, based on 100 percent of the weight of the composition and exclusive of any water and/or ammonia present,
a) greater than about 3.0 weight percent of the combination of TETA and TEPA,
b) greater than about 0.1 weight percent of TEPA,
c) greater than about 3.0 weight percent of TETA,
d) less than about 90.0 weight percent of DETA and/or EDA,
e) less than about 90.0 weight percent of MEA and/or AEEA,
f) less than about 12.5 weight percent of the combination of PIP and AEP,
g) less than about 15.0 weight percent of other polyalkylene polyamines,
h) a TETA+TAEA to PIP+AEP+PEEDA+DAEP+DPE weight ratio of greater than about 0.5,
i) a TEPA+AETAEA to PIP+AEP+PEEDA+DAEP+DPE+AEPEEDA+iAEPEEDA+AEDAEP+AEDPE+BPEA weight ratio of greater than about 0.5,
j) a TETA to TAEA weight ratio of greater than about 2.0, and
k) a TEPA to AETAEA weight ratio of greater than about 2.0.
The alkyleneamines producers composition of this invention can be subjected to conventional separations techniques for recovering the individual components of the composition. Such techniques are well known in the art and include, for example, distillation.
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 a metallic phosphate condensation catalyst having a cyclic structure or an acyclic structure which is transformed into a cyclic structure during the process. The metallic phosphate condensation catalysts embraced within the scope of this invention can be cyclic or a mixture of cyclic and acyclic and comprise structural units of the formula: ##STR1## wherein M is the same or different and is a substantially insoluble cation, X is the same or different and is oxygen, nitrogen or sulfur, and y is a value of from 1 to about 20 or greater. The preferred metallic phosphate condensation catalysts have a cyclic structure and ionic character and/or ion exchange capacity.
While not wishing to be bound to any particular theory, it is believed that those metallic phosphates encompassed within the scope of this invention having a cyclic structure and possessing ionic character and/or ion exchange capacity exhibit desired catalytic activity and provide desired product selectivity. While the reaction mixture may initially include one or more metallic phosphates other than metallic phosphates having a cyclic structure and possessing ionic character and/or ion exchange capacity, it is believed to be desirable that such metallic phosphates having a cyclic structure and possessing ionic character and/or ion exchange capacity be formed in situ in order to provide desired catalytic activity and product selectivity. In such instances, catalyst preparation conditions or the reaction conditions should allow for the formation of metallic phosphates having a cyclic structure and possessing ionic character and/or ion exchange capacity. Mixtures of metallic phosphates having a cyclic structure and possessing ionic character and/or ion exchange capacity with metallic phosphates having other than a cyclic structure and other than ionic character and/or ion exchange capacity are believed to exhibit desired catalytic activity and provide desired product selectivity.
In accordance with this invention, the metallic phosphate condensation catalyst has a cyclic structure or an acyclic structure which is capable of being transformed into a cyclic structure during the process. The metallic phosphate condensation catalyst can 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.sub.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 condensation catalysts in accordance with this invention. Suitable metals which can be incorporated into the metallic phosphate condensation catalyst 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.
Illustrative of metallic orthophosphate catalysts 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 pyrophosphate catalysts which may be utilized in this invention include, for example, Na.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 (NH.sub.4).sub.2 P.sub.2 O.sub.7, Ca.sub.32 Cu.sub.14 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 polyphosphate catalysts which may be utilized in this invention include, for example, NaSr.sub.2 P.sub.3 O.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 metaphosphate catalysts 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 Ni(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 ultraphosphate catalysts 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. The metallic phosphate condensation catalysts having an acyclic structure used herein should be capable of being transformed into a cyclic structure under the reaction conditions. The preferred metallic phosphate condensation catalysts for use in this invention include Group IA metal metaphosphates, Group IA meal dihydrogen orthophosphates and Group IA metal dihydrogen pyrophosphates, more preferably Na.sub.3 P.sub.3 O.sub.9, NaH.sub.2 PO.sub.4 and Na.sub.2 H.sub.2 P.sub.2 O.sub.7. Other suitable metallic phosphate condensation catalysts having a cyclic structure or an acyclic structure capable of being transformed into a cyclic structure during the process 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).
As indicated above, metallic phosphate condensation catalysts having an acyclic structure are suitable for use in the process of this invention provided that the acyclic structure is transformed into a cyclic structure during the reaction. Suitable catalysts for use in the process of this invention include metallic phosphates having a cyclic structure, metallic phosphates having an acyclic structure which are transformed into a cyclic structure during the reaction and mixtures of metallic phosphates having a cyclic structure with metallic phosphates having an acyclic structure which may or may not transform into a cyclic structure during the reaction it is recognized that any combination of metallic phosphates may be used in the process of this invention provided at least one metallic phosphate having a cyclic structure is present during the reaction. It is also recognized that metallic phosphates having a cyclic structure can be formed under reaction conditions from any combination of metallic phosphates having an acyclic structure and/or cyclic structure or other reactants in the process.
The metallic phosphate condensation catalysts can be prepared by conventional methods known in the art. Sodium is believed to be one of a small group of cations effective for stabilizing six-membered cyclic metaphosphates at their temperatures of fusion (about 625.degree. C.) without decomposition to linear and/or other phosphates including mixtures. The formation of cyclic and acyclic metallic phosphate structures appears to depend on the cation ionic size, the coordination number of the cation and the ionic or covalent nature of the metal-oxygen bond.
The level of activity of the metallic phosphate 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, supported metallic phosphate condensation catalysts should have 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 metal oxide described below 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 metallic phosphate condensation catalyst and the performance moderators described below can affect the surface area of the metallic phosphate condensation catalyst. While surface areas described above may be preferred, for purposes of this invention, the surface area of the metallic phosphate condensation catalyst should be sufficient to contribute to product selectivity, catalytic activity and/or mechanical or dimensional strength of the catalyst.
The metallic phosphate condensation catalysts useful in this invention can be associated with one or more metal oxides. Preferred metal oxides are amphoteric or slightly acidic or slightly basic. Illustrative of such metal oxides which may be utilized in association with the metallic phosphate condensation 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 Group IVB metal oxides or mixtures thereof. Preferred metal oxides which may be utilized in association with the metallic phosphate condensation catalyst include, for example, one or more oxides of beryllium, scandium, yttrium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, tungsten, iron, cobalt, zinc, silver, aluminum, gallium, indium, silicon, germanium, tin, lead, arsenic, antimony and bismuth.
Group IVA and IVB metal oxides such as silica, titanium dioxide and zirconium dioxide are preferred for use in this invention. 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 metallic phosphate component per se and can contribute to product selectivity and catalytic activity.
Illustrative of mixed metal oxides which may be used in association with the metallic phosphate catalyst 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 --NbO.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. 1064-1066 (1974).
The metal oxides described herein which can be used in association with the metallic phosphate catalyst 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 90 percent or greater by weight of the metal oxide, preferably from about 0 to about 75 percent by weight of the metal oxide, and more preferably from about 0 to about 50 percent by weight of the metal oxide, the remainder being the weight of the metallic phosphate catalyst. 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 metallic phosphate condensation 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 metallic phosphate condensation catalyst of the invention provides sufficient activity to effect the condensation reaction, certain combinations of reactants and/or product formation may be 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. A range of suitable materials may impact the metallic phosphate condensation catalysts of this invention in the variety of reaction products. The performance moderator may be any material which impacts the metallic phosphate condensation catalyst's selection of reaction products or which changes the proportion of any one or more of the reaction products which the metallic phosphate condensation 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).
An illustrative 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 illustrative performance moderators include the metal oxides described above which can be used in association with the metallic phosphate condensation catalyst and also metallic phosphates which may or may not have a cyclic structure. Certain of these metallic phosphate performance moderators may also be effective as catalysts for use in this invention.
The metal oxides described hereinabove which can be used in association with the metallic phosphate catalyst 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).
As indicated above, other performance moderators which can be used in accordance with this invention include metallic phosphates which may or may not have a cyclic 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. Such metallic phosphates can contribute to product selectivity, catalytic activity and/or catalyst stability (mechanical strength).
Other performance moderators which can be used in accordance with this invention include metallic polyphosphates which may or may not have a condensed structure. 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. 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. Illustrative metallic polyphosphates having a condensed structure include many of the metallic phosphates described above.
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 metallic phosphate 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 metallic phosphate catalyst is not narrowly critical. Generally, the amount does not exceed 90 weight percent of the weight of the catalyst. The amount of performance moderator can range from about 0 to about 90 or greater weight percent of the weight of the catalyst, preferably from about 0 to about 75 weight percent of the weight of the catalyst, and more preferably from about 0 to about 50 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 25 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 are disclosed 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 metallic phosphate 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 metallic phosphate 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 metallic phosphate catalyst of the invention may be utilized as solid powders or as fused, bonded or compressed solid pellets, or larger structures in association with the one or more metal oxides, or as coated, fused, bonded or compressed solid pellets, or larger structures, composited with one or more support materials, in association with one or more metal oxides. 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 metallic phosphate catalyst 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 metal oxide in association with the metallic phosphate catalyst. Normally the drying temperature will be greater than about 120.degree. C. and below about 600.degree. C. depending on the thermal stability of the catalyst. 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 metallic phosphate catalyst in association with one or more metal oxides. For example, one or more metal oxides may be condensed from their respective hydrolyzable monomers to the desired oxides to form oxide powders which can thereafter be blended and compressed with the metallic phosphate to form pellets and larger structures of the metal oxide-containing condensation catalyst of this invention. The one or more metal oxides which can be used in association with the metallic phosphate catalyst in accordance with this invention can be provided from metal salts which can be heated to form the metal oxide. It is appreciated that the performance moderator can be incorporated into the molecular bonding configuration of the metal oxide-containing condensation catalyst by conventional procedures known in the art.
The metallic phosphate condensation catalysts in association with one or more metal oxides prior to the optional treatment of the performance moderator may be prepared in a wide variety of ways. For example, one or more metal oxides may be provided as a partial condensate on a support, such as a silica or alpha, beta or gamma alumina, silicon carbide, and the like, and then condensed by heating to effect polymerization to the desired oxide form. The metal oxide(s) may be condensed from hydrolyzable monomers to the desired oxide, indeed, to form an oxide powder which can thereafter be compressed in the presence of a metallic phosphate to form pellets and larger structures of the metal oxide-containing condensation catalyst of the invention. A blend of the powder and metallic phosphate 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 metallic phosphate 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 metal oxide-containing catalyst to the support.
In a preferred embodiment of this invention, a high surface area silica or titania can be slurried with an aqueous solution of sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate or sodium trimetaphosphate, extruded, and calcined at a temperature of about 400.degree. C.
A preferred catalyst structure comprises sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate or sodium trimetaphosphate in association with a Group IVA or IVB metal oxide having a surface area of at least a 140 m.sup.2 /gm which may or may not be 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 catalyst and is at least as stable as the catalyst to the reaction medium. The support can function as an amine condensation catalyst independent of the metallic phosphate having a cyclic structure, although it may have lower catalytic activity to the reaction. The support may act in concert with the catalyst to moderate the reaction. Some supports may contribute to the selectivity of the reaction. The catalyst structure can comprise from about 2 to about 60 percent by weight or greater of the support, more preferably from about 10 to about 50 percent by weight of the support, the remainder being the weight of the metal oxide(s) and metallic phosphate. 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 metallic phosphate and/or 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 metallic phosphate and one or more metal oxides or a partial condensate thereof. The paste may comprise the oxide forms of the support and the metallic phosphate, 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 sizes. 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 metal oxide-containing condensation catalyst.
The use of supports for the metallic phosphate condensation catalyst provides a number of significant advantages. It has been determined that some of the metallic phosphates 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 metallic phosphate 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--aminoethyltrisaminoethylamine
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.
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 metallic phosphate 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______________________________________
The process of the invention provides the ability to generate the manufacture of desirable higher polyalkylene polyamine products such as TETA, TEPA and PEHA without generating large amounts of cyclic alkylenepolyamine products such as PIP, AEP and HEP. The alkyleneamines producers composition of this invention has a TETA+TAEA to PIP+AEP+PEEDA+DAEP+DPE weight ratio of greater than about 0.5, a TETA to TAEA weight ratio of greater than about 2.0 and a TEPA to AETAEA weight ratio of greater than about 2.0.
The process of this invention provides the potential to control congener distribution, linear to cyclic selectivity and linear to branched selectivity of the higher polyalkylene polyamines.
It is appreciated that the metallic phosphate 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 metallic phosphate condensation catalyst having a cyclic structure or an acyclic structure which is transformed into a cyclic structure during the process under conditions effective to produce alkylamines.
This invention is further illustrated by certain of the following examples:
EXAMPLES
In the examples set forth in the tables below, the catalyst of choice was placed in one of three tubular reactors, each having an outside diameter of 1 inch and an overall length of 24 inches. The catalyst portion of the reactor was sufficient for accommodating 100 cubic centimeters of catalyst. The reactor was made of 316 stainless steel. As used herein, ABl 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 (<=N4) refers to the weight ratio of TETA+TAEA to PIP+AEP+PEEDA+DAEP+DPE. The catalysts employed are identified as follows:
______________________________________Designation Composition Physical Properties______________________________________A Titanium dioxide Particle size: 1/16 (anatase)/sodium inch cylindrical trimetaphosphate; extrudates; Catalyst Ti:P atom ratio = surface area: 133.3 5.7:1 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.B Titanium dioxide Particle size: 1/16 (anatase)/sodium inch cylindrical tripolyphosphate; extrudates; Catalyst Ti:P atom ratio = surface area: 80.3 5.7:1 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.C Titanium dioxide Particle size: 1/16 (anatase)/AB1; inch cylindrical Ti:P atom ratio = extrudates; Catalyst 5.7:1 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.D Titanium dioxide Particle size: 1/16 (anatase)/sodium inch cylindrical pyrophosphate; extrudates; Catalyst Ti:P atom ratio = surface area: 78.6 5.7:1 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.E Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical boric acid (2 extrudates; Catalyst wt. %) surface area: 97.1 m.sup.2 /gm; Pore volume N.sub.2 : 0.440 cc/gm; Pore area: 84.2 m.sup.2 /gm; Bulk density: 1.32 gm/cc.F Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical ammonium tetra- extrudates; Catalyst fluoroborate surface area: 39.6 (2 wt. %) m.sup.2 /gm; Pore volume N.sub.2 : 0.442 cc/gm; Pore area: 66.7 m.sup.2 /gm; Bulk density: 1.34 gm/cc.G Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical sodium tetra- extrudates; Catalyst fluoroborate surface area: 44.1 (8 wt. %) m.sup.2 /gm; Pore volume N.sub.2 : 0.432 cc/gm; Pore area: 69.1 m.sup.2 /gm; Bulk density: 1.35 gm/cc.H Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical sodium tetra- extrudates; Catalyst fluoroborate surface area: 23.0 (8 wt. %) m.sup.2 /gm; Pore volume N.sub.2 : 0.373 cc/gm; Pore area: 36.6 m.sup.2 /gm; Bulk density: 1.57 gm/cc.I Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical sodium meta- extrudates; Catalyst tungstate surface area: 91.3 (1 wt. %) m.sup.2 /gm; Pore volume N.sub.2 : 0.414 cc/gm; Pore area: 75.7 m.sup.2 /gm; Bulk density: 1.40 gm/ccJ Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical sodium meta- extrudates; Catalyst tungstate surface area: 101.2 (2 wt. %) m.sup.2 /gm; Pore volume N.sub.2 : 0.442 cc/gm; Pore area: 94.2 m.sup.2 /gm; Bulk density: 1.38 gm/cc.K Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical sodium meta- extrudates; Catalyst tungstate surface area: 100.2 (4 wt. %) m.sup.2 /gm; Pore volume N.sub.2 : 0.429 cc/gm; Pore area: 90.0 m.sup.2 /gm; Bulk density: 1.43 gm/cc.L Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical ammonium meta- extrudates; Catalyst tungstate surface area: 97.9 (2 wt. % as WO.sub.3) m.sup.2 /gm; Pore volume N.sub.2 : 0.431 cc/gm; Pore area: 79.4 m.sup.2 /gm; Bulk density: 1.43 gm/cc.M Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical ammonium meta- extrudates; Catalyst tungstate surface area: 91.8 (4 wt. % as WO.sub.3) m.sup.2 /gm; Pore volume N.sub.2 : 0.402 cc/gm; Pore area: 69.2 m.sup.2 /gm; Bulk density: 1.51 gm/cc.N Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical ammonium meta- extrudates; Catalyst tungstate surface area: 78.1 (8 wt. % as WO.sub.3) m.sup.2 /gm; Pore volume N.sub.2 : 0.403 cc/gm; Pore area: 74.0 m.sup.2 /gm; Bulk density: 1.47 gm/cc.O Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical lanthanum oxide extrudates; Catalyst (2 wt. %) surface area: 102.8 m.sup.2 /gm; Pore volume N.sub.2 : 0.409 cc/gm; Pore area: 65.3 m.sup.2 /gm; Bulk density: 1.49 gm/cc.P Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical lanthanum oxide extrudates; Catalyst (4 wt. %) surface area: 102.6 m.sup.2 /gm; Pore volume N.sub.2 : 0.418 cc/gm; Pore area: 85.4 m.sup.2 /gm; Bulk density: 1.41 gm/cc.Q Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical niobium oxide extrudates; Catalyst (2 wt. %) surface area: 102.8 m.sup.2 /gm; Pore volume N.sub.2 : 0.435 cc/gm; Pore area: 85.5 m.sup.2 /gm; Bulk density: 1.35 gm/cc.R Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical sodium bicarbonate extrudates; Catalyst (2 wt. %) surface area: 99.5 m.sup.2 /gm; Pore volume N.sub.2 : 0.417 cc/gm; Pore area: 76.4 m.sup.2 /gm; Bulk density: 1.41 gm/cc.S Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical vanadium oxide extrudates; Catalyst (2 wt. %) surface area: 88.7 m.sup.2 /gm; Pore volume N.sub.2 : 0.411 cc/gm; Pore area: 63.9 m.sup.2 /gm; Bulk density: 1.44 gm/cc.T Titanium dioxide Particle size: 1/16 (anatase)/SiO.sub.2 / inch cylindrical Al.sub.2 O.sub.3 /sodium extrudates; Catalyst trimetaphosphate surface area: 129.9 (10 wt. %) m.sup.2 /gm; Pore volume N.sub.2 : 0.321 cc/gm; Pore area: 163 m.sup.2 /gm; Bulk density: 1.59 gm/cc.U Titanium dioxide Particle size: 1/16 (anatase)/SiO.sub.2 / inch cylindrical B.sub.2 O.sub.3 /sodium extrudates; Catalyst trimetaphosphate surface area: 159.5 (10 wt %) m.sup.2 /gm; Pore volume N.sub.2 : 0.312 cc/gm; Pore area: 129.8 m.sup.2 /gm, Bulk density: 1.54 gm/cc.V Titanium dioxide Particle size: 1/16 (anatase)/SiO.sub.2 / inch cylindrical sodium trimeta- extrudates; Catalyst phosphate surface area: 136.5 (10 wt %) m.sup.2 /gm; Pore volume N.sub.2 : 0.399 cc/gm; Pore area: 162.5 m.sup.2 /gm; Bulk density: 1.48 gm/cc.W Titanium dioxide/ Particle size: 1/16 AB1 inch cylindrical extrudates; Catalyst surface area: 4.40 m.sup.2 /gm; Pore volume N.sub.2 : 0.184 cc/gm; Pore area: 19.2 m.sup.2 /gm; Bulk density: 2.10 gm/cc.X Titanium dioxide Particle size: 1/16 (anatase)/AB1 inch cylindrical extrudates; Catalyst surface area: 102.0 m.sup.2 /gm; Pore volume N.sub.2 : 0.406 cc/gm; Pore area: 68.6 m.sup.2 /gm; Bulk density: 1.43 gm/cc.Y Maqnesium oxide/ Particle size: 1/16 AB1 inch cylindrical extrudates; Catalyst surface area: 18.1 m.sup.2 /gm; Pore volume N.sub.2 : 0.298 cc/gm; Pore area: 52.9 m.sup.2 /gm; Bulk density: 1.78 gm/cc.Z Silicon dioxide/ Particle size: 1/16 AB1 inch cylindrical extrudates; Catalyst surface area: 33.7 m.sup.2 /gm; Pore volume N.sub.2 : 0.496 cc/gm; Pore area: 81.0 m.sup.2 /gm; Bulk density: 1.06 gm/cc.AA Aluminum oxide/ Particle size: 1/16 lanthanum meta- inch cylindrical phosphate extrudates; Catalyst surface area: 86.0 m.sup.2 /gm; Pore volume N.sub.2 : 0.327 cc/gm; Pore area: 129.5 m.sup.2 /gm; Bulk density: 1.57 gm/cc.BB Silicon dioxide/ Particle size: 1/16 lanthanum meta- inch cylindrical phosphate extrudates; Catalyst surface area: 38.7 m.sup.2 /gm; Pore volume N.sub.2 : 0.656 cc/gm; Pore area: 90.5 m.sup.2 /gm; Bulk density: 0.99 gm/cc.CC Titanium dioxide Particle size: 1/16 (anatase)/AB1/ZnO inch cylindrical (2 wt. %) extrudates; Catalyst surface area: 90.4 m.sup.2 /gm; Pore volume N.sub.2 : 0.427 cc/gm; Pore area: 74.5 m.sup.2 /gm; Bulk density: 1.49 gm/cc.DD Titanium dioxide Particle size: 1/16 (anatase)/AB1/ZnO inch cylindrical (4 wt. %) extrudates; Catalyst surface area: 78.3 m.sup.2 /gm; Pore volume N.sub.2 : 0.412 cc/gm; Pore area: 75.1 m.sup. 2 /gm; Bulk density: 1.42 gm/cc.EE Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical Nb.sub.2 O.sub.5 extrudates; Catalyst (4 wt. %) surface area: 102.2 m.sup.2 /gm; Pore volume N.sub.2 : 0.407 cc/gm; Pore area: 75.4 m.sup.2 /gm; Bulk density: 1.44 gm/cc.FF Titanium dioxide Particle size: 1/16 (anatase)/AB1/ inch cylindrical NaBF.sub.4 (8 wt. %) extrudates; Catalyst surface area: 22.5 m.sup.2 /gm; Pore volume N.sub.2 : 0.421 cc/gm; Pore area: 55.8 m.sup.2 /gm; Bulk density: 1.38 gm/cc.GG Titanium dioxide Particle size: (anatase)/sodium 1/16 inch cylindri- dihydrogen phos- cal extrudates; phate; Ti:P atom Catalyst surface ratio = 5.7:1 area: 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.HH Titanium dioxide Particle size: 1/16 (anatase)/disodium inch cylindrical dihydrogen pyro- extrudates; Cata- phosphate; Ti:P lyst surface area: atom ratio = 133.5 m.sup.2 /gm; Pore 5.7:1 N.sub.2 : 0.291 cc/gm; Pore area: 89.6 m.sup.2 /gm; Bulk denisity: 1.66 gm/cc.II Titanium dioxide Particle size: 1/16 (anatase)/disodium inch cylindrical hydrogen phosphate; extrudates; Cata- Ti:P atom ratio = lyst surface area: 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.JJ Titanium dioxide Particle size: 1/16 (anatase)/sodium inch cylindrical phosphate; Ti:P extrudates; Catalyst atom ratio = surface area: 88.4 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 DETA-MEA feed. After a sufficient line out period, a two hour timed run was conducted and a sample taken. The temperature was then adjusted for the next experiment. The above procedure was repeated for each of the examples.
The catalysts employed in the examples hereinafter were prepared as follows:
Catalyst A: Obtained from Norton Company, Akron, Ohio
Catalyst B: Obtained from Norton Company, Akron, Ohio.
Catalyst C: Obtained from Norton Company, Akron, Ohio.
Catalyst D: Obtained from Norton Company, Akron, Ohio.
Catalyst E: Catalyst C pellets (140 grams) were added to a solution of boric acid (5.07 grams) in methanol (94.2 grams). The methanol was removed using a Buchi rotary 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 F: Catalyst C pellets (140 grams) were added to a solution of ammonium tetrafluoroborate (2.86 grams) in water Enough solution was prepared to completely wet the pellets. The resulting slurry was allowed to stand 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 G: Catalyst C pellets (140.1 grams) were added to a solution of sodium tetrafluoroborate (8.58 grams) in sufficient water to completely wet the pellets. The catalyst was dried at a temperature of 100.degree. C. for a period 1 hour and then calcined at a temperature of 400.degree. C. for a period of 16 hours.
Catalyst H: Catalyst C pellets (140.1 grams) were added to a solution of sodium tetrafluoroborate (8.58 grams) in sufficient water to completely wet the pellets. 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 I: Catalyst C pellets (140.2 grams) were added to a solution of sodium metatungstate (1.43 grams) in sufficient water to completely wet the pellets. 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 J: Catalyst C pellets (140.2 grams) were added to a solution of sodium metatungstate (2.86 grams) in sufficient water to completely wet the pellets. 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 K: Catalyst C pellets (140.1 grams) were added to a solution of sodium metatungstate (5.71 grams) in sufficient water to completely wet the pellets. 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 L: Catalyst C pellets (140.1 grams) were added to a solution of ammonium metatungstate (3.12 grams) in sufficient water to completely wet the pellets. 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 M: Catalyst C pellets (140 grams) were added to a solution of ammonium metatungstate (6.24 grams) in sufficient water to completely wet the pellets. 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 N: Catalyst C pellets (140 1 grams) were added to a solution of ammonium metatungstate (12.48 grams) in sufficient water to completely wet the pellets. 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 O: Catalyst C pellets (140.1 rams) were added to a solution of lanthanum nitrate hexahydrate (7.59 grams) in sufficient water to completely wet the pellets. 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 P: Catalyst C pellets (143.1 grams) were added to a solution of lanthanum nitrate hexahydrate (15.18 grams) in sufficient water to completely wet the pellets. 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 Q: Catalyst C pellets (140 grams) were added to a solution of niobium pentethoxide (6.84 grams) in toluene (66 grams). Enough solution was added to completely immerse the pellets. The resulting slurry was stripped on a Buchi rotary evaporator. The catalyst was then calcined at a temperature of 400.degree. C. for a period of 16 hours.
Catalyst R: Catalyst C pellets (140.4 grams) were added to a solution of sodium bicarbonate (3.87 grams) in sufficient water to completely wet the pellets. 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 S: Catalyst C pellets (143.5 grams) were added to a solution of vanadium triisopropoxide (7.63 grams) in toluene (66.74 grams). Enough solution was added to completely wet the pellets. The resulting slurry was stripped under reduced pressure The catalyst was then calcined at a temperature of 400.degree. C. for a period of 16 hours.
Catalyst T: Sodium trimetaphosphate (14.0 grams) was dissolved in a sufficient amount of water (82.7 grams) to wet the TiO.sub.2 /SiO.sub.2 /Al.sub.2 O.sub.3 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 U: Sodium trimetaphosphate (14.13 grams) was dissolved in water (56.0 grams) and isopropanol (87.0 grams). 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 V: Sodium trimetaphosphate (14.05 grams) was dissolved in a sufficient amount of water (85.92 grams) to wet the TiO.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 W: Obtained from Norton Company. Akron, Ohio.
Catalsyt X: Obtained from Norton Company, Akron, Ohio.
Catalyst Y: Obtained from Norton Company, Akron, Ohio.
Catalyst Z: Obtained from Norton Company, Akron, Ohio.
Catalsyt AA: Obtained from Norton Company, Akron, Ohio.
Catalyst BB: Obtained from Norton Company, Akron, Ohio.
Catalyst CC: Catalyst C pellets (140.5 grams) were added to a solution of zinc nitrate hexahydrate (10.45 grams) in sufficient water to completely wet the pellets. 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 DD: Catalyst C pellets (140.78 grams) were added to a solution of zinc nitrate hexahydrate (20.88 grams) in sufficient water to completely wet the pellets. 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 EE: Catalyst C pellets (140.1 grams) were added to a solution of niobium pentethoxide (13.68 grams) in toluene (66.2 grams). Enough solution was added to completely immerse the pellets. The resulting slurry was allowed to stand for a 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 FF: Catalyst C pellets (140.15 grams) were added to a solution of sodium tetrafluoroborate (8.58 grams) in sufficient water to completely wet the pellets 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: Obtained from Norton Company, Akron, Ohio.
Catalyst HH: Obtained from Norton Company, Akron, Ohio.
Catalyst II: Obtained from Norton Company, Akron, Ohio.
Catalyst JJ: Obtained from Norton Company, Akron, Ohio.
TABLE I__________________________________________________________________________Example No. 1 2 3 4 5 6 7 8 9Catalyst Type A A A A A A A A A__________________________________________________________________________Catalyst weight, gm 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 603Temperature, .degree.C. 270 270 280 269 259 280 280 270.1 270Time on organics, hrs. 4.5 4.5 28.5 51.5 71.5 76.5 100.5 120 167.5Duration of run, hrs. 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 3.81DETA/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 0.874 1.232 1.585 0.847 0.433 1.400 1.565 0.773 0.551MEA 12.473 11.945 7.517 13.370 17.877 6.436 7.199 12.823 16.111PIP 0.965 1.116 1.414 1.070 0.651 1.400 1.451 1.028 0.807DETA 39.228 39.867 35.453 41.854 47.014 35.668 35.534 41.213 44.005AEEA 1.227 1.108 0.479 1.371 2.399 0.486 0.502 1.388 1.922AEP 1.183 1.533 1.814 1.158 0.708 1.977 1.886 1.126 0.824HEP 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 2.5601-TETA 12.867 13.297 13.364 12.613 12.062 14.170 13.658 12.943 12.257DAEP 0.519 0.744 0.968 0.425 0.180 1.018 0.985 0.432 0.232PEEDA 0.110 0.111 0.154 0.082 0.152 0.059 0.710 0.336 0.206DPE 0.118 0.120 0.127 0.085 0.097 0.087 0.322 0.227 0.120AE-TAEA 4.110 3.926 4.516 3.704 2.640 4.497 4.572 3.788 3.0141-TEPA 7.436 7.679 8.979 7.093 5.411 8.403 9.298 7.467 6.239AE-DAEP 0.140 0.117 0.182 0.100 0.097 0.000 0.808 0.390 0.275AE-PEEDA 0.099 0.100 0.129 0.096 0.000 0.720 0.173 0.127 0.099iAE-PEEDA 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 0.467BPEA 0.639 0.578 0.844 0.573 0.045 0.211 1.060 0.835 0.435Others 8.068 6.841 11.264 5.414 2.775 11.735 8.190 6.222 3.695MEA conversion, % 66.60 68.06 79.87 63.84 52.17 82.68 80.79 66.20 56.64DETA conversion, % 37.56 36.64 43.59 32.72 25.25 42.94 43.64 35.44 29.62Acyclic(N4), wt. % 95.43 94.25 92.75 96.27 97.15 93.54 88.94 94.00 96.37Acyclic(N5), wt. % 90.71 92.25 90.26 92.08 97.50 92.20 81.92 84.33 87.88.SIGMA. (N5)/.SIGMA.(N4), weight ratio 0.78 0.74 0.87 0.74 0.55 0.78 0.93 0.80 0.68Acyclic(N4)/cyclic(<=N4), 5.40 4.41 3.57 5.41 8.18 3.71 3.03 4.96 6.77weight ratio__________________________________________________________________________Example No. 10 11 12 13 14 15 16 17 18Catalyst Type A A A A A A A A A__________________________________________________________________________Catalyst weight, gm 78.74 78.74 78.74 78.74 78.74 78.74 78.74 78.74 78.74Pressure, psig 603 604 603 604 603 603 603 604 604Temperature, .degree.C. 280 259 269 260 280 270 280 270 270Time on organics, hrs. 172.5 191.5 196.5 214.5 219.5 238.5 243.5 262.5 266Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.71 3.89 3.89 3.81 3.78 3.79 3.51 3.51 3.71DETA/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 1.445 0.461 0.791 0.658 1.456 0.910 1.122 1.072 1.017MEA 5.976 18.787 12.858 18.141 6.956 13.064 13.239 11.990 12.608PIP 1.387 0.691 1.023 0.811 1.416 1.148 1.024 1.234 1.186DETA 33.430 47.586 40.957 45.580 35.955 41.603 42.624 40.482 40.928AEEA 0.443 2.282 1.404 1.879 0.493 1.322 1.350 1.216 1.269AEP 1.827 0.682 1.103 0.881 1.832 1.184 1.192 1.267 1.191HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.553 2.310 2.681 2.359 2.571 2.654 2.361 2.647 2.6271-TETA 13.506 10.647 12.732 10.997 13.341 12.720 11.438 12.833 12.755DAEP 1.004 0.173 0.386 0.275 0.888 0.410 0.490 0.472 0.422PEEDA 0.710 0.146 0.310 0.222 0.654 0.336 0.382 0.369 0.339DPE 0.335 0.085 0.184 0.086 0.309 0.196 0.271 0.070 0.135AE-TAEA 4.645 2.372 3.629 2.706 4.368 3.735 3.951 3.951 3.7511-TEPA 9.538 4.500 6.990 5.378 8.945 7.412 6.576 7.610 7.246AE-DAEP 0.848 0.213 0.276 0.183 0.700 0.300 0.385 0.331 0.291AE-PEEDA 0.185 0.000 0.057 0.056 0.084 0.065 0.085 0.035 0.028iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 1.089 0.315 0.667 0.434 1.016 0.698 0.091 0.064 0.062BPEA 1.026 0.247 0.634 0.403 0.932 0.638 0.093 0.594 0.053Others 9.232 1.904 3.598 2.311 6.162 3.686 6.348 5.045 5.231MEA conversion, % 83.70 48.64 64.40 50.59 80.69 64.55 64.31 67.22 65.36DETA conversion, % 45.82 22.68 32.60 26.22 40.67 32.91 31.71 34.22 33.16Acyclic(N4), wt. % 88.68 96.98 94.60 95.81 89.58 94.23 92.35 94.45 94.49Acyclic(N5), wt. % 81.83 89.87 86.66 88.25 82.97 86.76 94.15 91.86 96.21.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.96 0.57 0.75 0.66 0.90 0.79 0.75 0.77 0.70Acyclic(N4)/cyclic(<=N4), 3.05 7.29 5.13 5.86 3.12 4.70 4.11 4.54 4.70weight ratio__________________________________________________________________________
TABLE II__________________________________________________________________________Example No. 19 20 21 22 23 24 25 26 27Catalyst Type B B B B B B B B B__________________________________________________________________________Catalyst weight, gm 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 603Temperature, .degree.C. 270 270 280 259 269 259 280 280 270.1Time on organics, hrs. 4.5 23.5 28.5 47.5 51.5 71.5 76.5 100.5 120Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 2.95 2.82 2.91 2.90 2.89 2.81 2.72 2.85 2.92DETA/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 0.387 0.451 0.942 0.263 0.472 0.251 0.768 0.805 0.481MEA 18.211 18.550 12.561 24.117 18.908 22.270 11.181 11.851 17.815PIP 0.711 0.768 1.105 0.411 0.731 0.450 1.013 1.082 0.763DETA 45.762 47.529 39.025 52.023 46.902 51.519 38.122 38.925 46.516AEEA 1.902 2.077 1.192 2.582 2.111 2.804 1.247 1.088 2.005AEP 0.846 0.787 1.214 0.446 0.718 0.519 1.229 1.254 0.767HEP 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 2.3451-TETA 10.921 11.106 12.012 8.125 11.140 9.812 13.613 12.691 11.657DAEP 0.186 0.202 0.477 0.080 0.175 0.097 0.523 0.523 0.191PEEDA 0.159 0.178 0.147 0.057 0.157 0.084 0.424 0.443 0.174DPE 0.084 0.096 0.095 0.052 0.114 0.086 0.094 0.303 0.105AE-TAEA 2.341 2.390 3.575 1.205 2.444 1.558 4.042 3.853 2.6501-TEPA 3.918 5.171 7.286 2.186 6.082 3.822 8.123 8.109 6.868AE-DAEP 0.366 0.189 0.131 0.129 0.081 0.000 0.417 0.508 0.093AE-PEEDA 0.080 0.079 0.101 0.068 0.000 0.000 0.113 0.139 0.000iAE-PEEDA 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 0.055BPEA 0.328 0.276 0.649 0.076 0.291 0.128 0.215 0.930 0.371Others 6.126 2.669 9.532 1.845 2.513 1.388 8.524 7.390 2.594MEA conversion, % 51.16 50.15 66.20 34.36 49.36 40.71 70.01 68.44 52.59DETA conversion, % 27.06 24.09 37.59 15.85 25.35 18.49 39.22 38.40 26.43Acyclic(N4), wt. % 96.80 96.56 95.26 98.11 96.78 97.79 94.03 92.26 96.75Acyclic(N5), wt. % 84.17 92.59 90.47 91.27 94.99 96.53 92.65 83.44 94.83.SIGMA. (N5)/.SIGMA.(N4), weight ratio 0.56 0.59 0.79 0.37 0.65 0.46 0.75 0.87 0.69Acyclic(N4)/cyclic(<=N4), 6.52 6.58 4.75 9.37 7.08 9.58 4.99 4.20 7.00weight ratio__________________________________________________________________________Example No. 28 29 30 31 32 33 34 35 36 37Catalyst Type B B B B B B B B B B__________________________________________________________________________Catalyst weight, gm 84.66 84.66 84.66 84.66 84.66 84.66 84.66 84.66 84.66 84.66Pressure, psig 598 598 598 598 598 599 599 604 604 604Temperature, .degree.C. 270 280 259 269 260 280 270 280 270 270Time on organics, hrs. 167.5 172.5 191.5 196.5 214.5 219.5 238.5 243.5 262.5 266Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 2.92 2.51 2.94 2.91 3.37 2.82 2.90 2.83 2.69 2.83DETA/MEA mole ratio 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 5.97Crude product composition, wt. %EDA 0.768 0.935 0.259 0.554 0.303 0.984 0.731 1.166 0.772 0.727MEA 11.617 9.895 22.504 16.654 25.518 10.278 15.594 9.688 14.486 15.223PIP 1.012 1.112 0.501 0.801 0.351 1.163 0.969 1.258 0.984 0.967DETA 38.660 37.291 50.906 44.882 53.431 38.532 43.211 37.652 42.240 43.621AEEA 1.321 0.909 2.608 1.955 2.502 0.852 1.707 0.755 1.601 1.652AEP 1.097 1.308 0.480 0.827 0.406 1.361 1.004 1.440 1.010 0.980HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.638 2.623 2.028 2.607 1.424 2.641 2.659 2.671 2.744 2.6661-TETA 12.643 12.534 9.067 11.734 6.423 12.393 11.936 12.701 12.439 12.081DAEP 0.461 0.560 0.119 0.241 0.079 0.538 0.298 0.622 0.320 0.282PEEDA 0.353 0.455 0.081 0.211 0.068 0.431 0.263 0.498 0.276 0.248DPE 0.353 0.332 0.103 0.133 0.127 0.308 0.161 0.109 0.118 0.100AE-TAEA 3.917 4.248 1.719 2.992 1.105 4.215 3.423 4.647 3.605 3.4111-TEPA 8.051 8.471 3.147 5.870 1.995 8.144 6.762 8.696 6.609 6.249AE-DAEP 0.479 0.536 0.073 0.161 0.074 0.499 0.236 0.581 0.204 0.181AE-PEEDA 0.163 0.150 0.064 0.000 0.053 0.132 0.054 0.123 0.034 0.030iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.793 0.918 0.151 0.456 0.092 0.892 0.536 0.306 0.061 0.063BPEA 0.949 1.033 0.115 0.459 0.108 0.885 0.576 0.724 0.059 0.402Others 7.450 7.630 1.713 2.553 2.042 6.020 3.491 7.953 4.671 3.839MEA conversion, % 68.95 73.17 39.26 54.71 30.82 71.85 58.06 73.87 60.45 58.58DETA conversion, % 38.60 39.91 18.34 27.46 13.91 37.28 30.93 39.64 31.46 29.46Acyclic(N4), wt. % 92.90 91.84 97.34 96.08 96.64 92.17 95.29 92.60 95.51 95.90Acyclic(N5), wt. % 83.45 82.83 92.34 89.17 90.46 83.69 87.90 88.50 96.63 93.47.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.88 0.93 0.46 0.67 0.42 0.91 0.76 0.91 0.67 0.67Acyclic(N4)/cyclic(<=N4), 4.66 4.02 8.64 6.48 7.62 3.95 5.42 3.91 5.61 5.72weight ratio__________________________________________________________________________
TABLE III__________________________________________________________________________Example No. 38 39 40 41 42 43 44 45 46Catalyst Type C C C C C C C C C__________________________________________________________________________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, gmol/hr/kgcat 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 2.1951-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 2.0911-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 IV__________________________________________________________________________Example No. 47 48 49 50 51 52 53 54 55Catalyst Type D D D D D D D D D__________________________________________________________________________Catalyst weight, gm 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 602Temperature, .degree.C. 270 270 280 259 269 259 280 280 270.1Time on organics, hrs. 4.5 23.5 28.5 47.5 51.5 71.5 76.5 100.5 120Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.96 3.87 4.09 3.96 3.90 3.87 3.92 3.90 4.03DETA/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 0.223 0.361 0.675 0.212 0.396 0.180 0.730 0.795 0.461MEA 24.445 22.069 16.449 26.799 21.362 24.727 13.740 14.037 20.260PIP 0.470 0.526 0.892 0.297 0.553 0.298 0.888 0.897 0.585DETA 53.878 51.806 46.950 56.278 50.889 55.710 44.046 42.839 49.907AEEA 2.281 2.479 1.818 2.578 2.565 2.914 1.871 1.449 2.318AEP 0.515 0.624 1.064 0.387 0.663 0.447 1.193 1.137 0.672HEP 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 1.9311-TETA 7.238 7.768 10.879 5.638 8.217 6.704 12.235 11.091 9.032DAEP 0.092 0.160 0.324 0.058 0.188 0.079 0.480 0.476 0.204PEEDA 0.097 0.137 0.289 0.053 0.154 0.073 0.398 0.393 0.166DPE 0.075 0.095 0.046 0.052 0.063 0.100 0.355 0.333 0.191AE-TAEA 1.219 1.522 2.583 0.752 1.679 0.945 3.598 3.115 2.0031-TEPA 2.039 2.628 5.427 1.366 3.512 1.934 6.530 6.472 4.096AE-DAEP 0.173 0.187 0.318 0.000 0.179 0.087 0.390 0.491 0.208AE-PEEDA 0.066 0.063 0.068 0.000 0.071 0.080 0.096 0.129 0.079iAE-PEEDA 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 0.139BPEA 0.101 0.141 0.381 0.047 0.197 0.060 0.186 0.732 0.292Others 2.821 3.594 4.790 1.260 3.582 1.974 6.576 7.895 3.856MEA conversion, % 34.76 40.66 56.27 27.73 42.89 34.28 64.11 62.93 46.18DETA conversion, % 14.55 17.21 25.83 9.80 19.14 12.00 31.61 32.77 21.21Acyclic(N4), wt. % 97.05 96.00 95.18 97.67 96.10 96.98 92.27 91.72 95.13Acyclic(N5), wt. % 87.14 89.01 89.63 94.66 89.31 89.37 92.28 85.30 89.48.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.42 0.48 0.65 0.32 0.56 0.38 0.69 0.77 0.59Acyclic(N4)/cyclic(<=N4), 7.31 6.11 4.97 8.08 6.15 8.14 4.44 4.12 6.03weight ratio__________________________________________________________________________Example No. 56 57 58 59 60 61 62 63 64 65Catalyst Type D D D D D D D D D D__________________________________________________________________________Catalyst weight, gm 68.38 68.38 68.38 68.38 68.38 68.38 68.38 68.38 68.38 68.38Pressure, psig 602 602 603 602 603 603 602 603 603 603Temperature, .degree.C. 270 280 259 269 260 280 270 280 270 270Time on organics, hrs. 167.5 172.5 191.5 196.5 214.5 219.5 238.5 243.5 262.5 266Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.92 3.98 4.05 4.06 3.59 4.00 3.95 4.40 3.76 3.89DETA/MEA mole ratio 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 5.97Crude product composition, wt. %EDA 0.516 0.878 0.251 0.489 0.337 0.945 0.600 1.593 0.706 0.676MEA 18.745 12.739 24.769 19.980 21.647 14.371 19.473 6.716 18.311 19.235PIP 0.611 0.931 0.340 0.589 0.483 0.985 0.679 1.480 0.743 0.731DETA 47.493 41.921 53.539 49.348 49.438 44.879 48.790 36.170 47.421 48.217AEEA 2.331 1.424 2.555 2.352 2.505 1.539 2.260 0.475 2.170 2.155AEP 0.691 1.141 0.402 0.686 0.479 1.175 0.770 1.905 0.803 0.752HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.040 2.361 1.480 1.962 2.037 2.311 2.070 2.556 2.174 1.9901-TETA 9.416 11.410 6.735 8.956 8.928 10.980 9.466 13.448 10.036 9.225DAEP 0.223 0.454 0.082 0.179 0.113 0.411 0.216 0.992 0.260 0.214PEEDA 0.181 0.371 0.072 0.153 0.087 0.337 0.181 0.685 0.205 0.176DPE 0.211 0.323 0.103 0.188 0.090 0.336 0.229 0.084 0.151 0.130AE-TAEA 2.229 3.445 1.148 1.988 1.704 3.208 2.190 4.698 2.609 2.2551-TEPA 4.517 6.679 2.110 3.632 3.226 6.048 4.274 8.949 4.512 4.130AE-DAEP 0.250 0.419 0.072 0.068 0.065 0.302 0.149 0.729 0.156 0.129AE-PEEDA 0.091 0.113 0.055 0.000 0.051 0.055 0.000 0.083 0.027 0.026iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.100 0.642 0.059 0.074 0.169 0.596 0.296 0.104 0.073 0.070BPEA 0.316 0.649 0.081 0.221 0.152 0.558 0.257 0.781 0.053 0.056Others 4.550 5.879 1.898 3.066 1.779 4.582 3.140 7.552 4.192 3.803MEA conversion, % 49.40 65.33 32.69 45.43 40.15 61.44 47.63 81.50 50.64 47.61DETA conversion, % 23.81 32.19 13.53 19.90 18.77 28.43 22.01 40.80 24.03 21.95Acyclic(N4), wt. % 94.90 92.30 96.97 95.46 97.43 92.46 94.85 90.08 95.20 95.57Acyclic(N5), wt. % 89.91 84.74 92.45 93.93 91.87 85.96 90.20 88.94 95.85 95.78.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.62 0.80 0.42 0.52 0.48 0.75 0.59 0.86 0.58 0.57Acyclic(N4)/cyclic(<=N4), 5.98 4.28 8.23 6.09 8.76 4.10 5.56 3.11 5.65 5.60weight ratio__________________________________________________________________________
TABLE V__________________________________________________________________________Example No. 66 67 68 69 70 71 72 73 74Catalyst Type E E E E E E E E E__________________________________________________________________________Catalyst weight, gm 73.5 73.5 73.5 73.5 73.5 73.5 73.5 73.5 73.5Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 271.8 270 280.2 260.9 270.6 261.2 281.5 270 270Time on organics, hrs. 5 8.5 25 30 34 49 55 76 78Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.58 4.68 4.69 4.82 4.64 4.33 4.30 4.25 4.63DETA/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 1.589 2.650 2.164 0.505 0.958 0.544 2.028 0.834 1.373MEA 12.185 10.223 10.619 22.868 16.851 21.648 7.865 11.872 15.153PIP 1.766 1.979 2.007 0.826 1.277 0.872 2.020 1.302 1.673DETA 50.183 46.166 46.617 54.246 49.991 54.106 39.033 47.518 46.832AEEA 0.119 0.000 0.000 0.956 0.608 1.198 0.102 0.526 0.540AEP 2.179 2.940 2.249 0.787 1.410 0.884 2.331 1.655 1.577HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.287 2.018 2.378 1.970 2.298 2.027 2.600 2.786 2.0921-TETA 11.888 11.231 12.228 9.216 11.514 9.474 13.657 14.189 11.667DAEP 0.650 1.480 0.908 0.125 0.263 0.142 1.136 0.460 0.271PEEDA 0.395 0.990 0.562 0.087 0.186 0.092 0.793 0.320 0.185DPE 0.000 0.079 0.082 0.000 0.000 0.000 0.063 0.000 0.000AE-TAEA 2.483 2.485 2.951 1.171 2.213 1.284 3.723 3.229 2.1781-TEPA 5.189 5.996 6.225 2.266 4.333 2.454 8.413 6.752 4.536AE-DAEP 0.456 1.010 0.453 0.000 0.214 0.000 0.650 0.175 0.435AE-PEEDA 0.128 0.369 0.129 0.000 0.181 0.000 0.200 0.000 0.419iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.131 0.143 0.206 0.000 0.132 0.000 0.735 0.194 0.412BPEA 0.097 0.158 0.137 0.000 0.160 0.000 0.654 0.211 0.541Others 0.955 2.634 1.884 0.416 0.810 0.314 3.399 0.747 2.735MEA conversion, % 67.00 72.55 71.14 37.96 54.14 41.18 78.38 67.95 58.74DETA conversion, % 19.21 26.33 24.71 12.54 19.15 12.63 36.23 23.77 24.21Acyclic(N4), wt. % 93.14 83.87 90.40 98.14 96.85 98.00 89.08 95.60 96.79Acyclic(N5), wt. % 90.43 83.47 90.84 100.00 90.50 100.00 84.43 94.51 78.79.SIGMA. (N5)/.SIGMA.(N4), weight ratio 0.56 0.64 0.63 0.30 0.51 0.32 0.79 0.59 0.60Acyclic(N4)/cyclic(<=N4), 2.84 1.77 2.51 6.13 4.40 5.78 2.57 4.54 3.71weight ratio__________________________________________________________________________
TABLE VI__________________________________________________________________________Example No. 75 76 77 78 79 80 81 82 83Catalyst Type F F F F F F F F F__________________________________________________________________________Catalyst weight, gm 76.8 76.8 76.8 76.8 76.8 76.8 76.8 76.8 76.8Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 271.8 270 280.2 260.9 270.6 261.2 281.5 270 270Time on organics, hrs. 5 8.5 25 30 34 49 55 76 78Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.12 4.24 4.01 4.36 4.32 4.20 4.12 4.07 4.24DETA/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 0.668 1.225 4.618 0.557 0.985 0.575 1.947 0.795 1.103MEA 20.080 14.935 10.851 24.320 17.690 22.023 6.480 10.724 12.429PIP 0.842 1.211 3.467 0.742 1.218 0.827 1.830 1.251 1.391DETA 54.453 48.042 42.353 55.896 51.741 52.738 44.334 45.995 43.281AEEA 0.451 0.313 0.139 1.169 0.760 1.449 0.113 0.560 0.651AEP 0.974 1.563 4.537 0.688 1.325 0.757 2.402 1.604 1.454HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.048 2.361 1.079 1.584 2.048 1.917 2.309 2.717 2.2721-TETA 10.507 12.537 9.182 8.077 10.742 9.822 13.034 15.283 13.463DAEP 0.193 0.511 1.628 0.101 0.256 0.153 0.989 0.531 0.365PEEDA 0.122 0.327 1.082 0.000 0.173 0.087 0.592 0.336 0.226DPE 0.000 0.000 0.152 0.000 0.000 0.000 0.071 0.000 0.000AE-TAEA 1.448 2.895 1.930 0.722 1.679 1.331 3.231 3.219 2.9961-TEPA 2.807 6.158 3.803 1.591 3.499 2.971 7.631 7.644 6.601AE-DAEP 0.000 0.383 1.217 0.000 0.082 0.000 0.605 0.208 0.516AE-PEEDA 0.000 0.091 0.346 0.000 0.000 0.000 0.174 0.000 0.418iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.211 0.255 0.000 0.095 0.000 0.622 0.212 0.696BPEA 0.000 0.119 0.152 0.000 0.089 0.000 0.573 0.168 0.136Others 0.356 1.079 3.709 0.353 0.618 0.261 2.961 0.934 4.252MEA conversion, % 45.60 59.89 70.22 33.93 51.41 40.05 82.26 70.97 66.33DETA conversion, % 12.33 23.33 30.92 9.75 15.54 14.68 27.88 26.01 30.31Acyclic(N4), wt. % 97.56 94.68 78.19 98.96 96.75 97.99 90.27 95.40 96.38Acyclic(N5), wt. % 100.00 91.84 74.42 100.00 95.12 100.00 84.62 94.86 84.46.SIGMA.(N5)/.SIGMA. (N4), weight ratio 0.33 0.63 0.59 0.24 0.41 0.36 0.76 0.61 0.70Acyclic(N4)/cyclic(<=N4), 5.89 4.12 0.94 6.31 4.30 6.43 2.61 4.84 4.58weight ratio__________________________________________________________________________
TABLE VII__________________________________________________________________________Example No. 84 85 86 87 88 89 90 91Catalyst Type G G G G G G G G__________________________________________________________________________Catalyst weight, gm 76.9 76.9 76.9 76.9 76.9 76.9 76.9 76.9Pressure, psig 600 600 600 600 600 600 600 600Temperature, .degree.C. 274.4 274.4 280.9 259.8 270.6 259.9 281.6 270.4Time on organics, hrs. 22 26 45.5 50.5 69 74.5 95 119Duration of run, hrs. 2 2 2 2 2 2 2 1MEA SV, gmol/hr/kgcat 3.43 3.31 2.85 3.38 3.41 3.28 3.10 3.37DETA/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 1.637 1.752 6.215 1.030 1.705 0.900 2.931 2.193MEA 11.346 11.171 3.117 18.167 8.987 15.534 1.812 8.349PIP 0.000 1.648 4.753 1.076 1.772 1.117 2.704 1.830DETA 46.167 45.574 31.042 48.855 44.146 47.263 56.512 40.724AEEA 0.707 0.779 0.145 2.493 0.622 2.337 0.000 0.571AEP 1.861 1.810 7.515 1.125 2.031 1.205 4.394 2.315HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.681 2.785 1.354 2.334 2.745 2.609 1.349 2.5591-TETA 14.827 14.769 9.178 13.329 15.519 14.514 14.115 14.634DAEP 0.707 0.684 3.204 0.266 0.862 0.288 1.482 1.224PEEDA 0.445 0.480 2.063 0.161 0.535 0.170 0.741 0.805DPE 0.104 0.070 0.140 0.000 0.097 0.000 0.000 0.048AE-TAEA 2.754 2.700 1.519 1.536 2.882 1.909 0.548 2.6241-TEPA 6.335 6.366 3.932 3.904 7.086 4.851 1.430 7.214AE-DAEP 0.241 0.242 1.881 0.138 0.283 0.068 0.260 0.638AE-PEEDA 0.079 0.075 0.401 0.000 0.087 0.000 0.000 0.188iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.420 0.000 0.205 0.042 0.000 0.216BPEA 0.223 0.231 0.079 0.000 0.239 0.045 0.000 0.261Others 1.726 1.594 11.423 0.487 1.637 0.517 0.425 2.538MEA conversion, % 69.01 69.88 91.52 51.10 75.61 57.80 94.97 76.78DETA conversion, % 25.06 26.98 49.81 21.84 28.79 23.70 6.73 32.70Acyclic(N4), wt. % 93.31 93.43 66.08 97.35 92.43 97.40 87.43 89.22Acyclic(N5), wt. % 94.36 94.30 66.22 97.52 92.46 97.75 88.40 88.31.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.51 0.51 0.52 0.35 0.55 0.39 0.13 0.58Acyclic(N4)/cyclic(<=N4), 5.62 3.74 0.60 5.96 3.45 6.16 1.66 2.76weight ratio__________________________________________________________________________
TABLE VIII__________________________________________________________________________Example No. 92 93 94 95 96 97 98Catalyst Type H H H H H H H__________________________________________________________________________Catalyst weight, gm 79.56 79.56 79.56 79.56 79.56 79.56 79.56Pressure, psig 602 602 603 602 602 603 603Temperature, .degree.C. 268.2 270 280 258 270 279.6 269.3Time on organics, hrs. 24 4.5 29 48 72 77 96.25Duration of run, hrs. 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 1.40 2.14 0.94 0.90 2.37 1.20 0.78DETA/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 1.357 2.006 4.277 2.306 1.090 3.199 2.846MEA 3.284 1.883 0.923 5.261 9.399 1.511 0.959PIP 1.251 1.346 2.162 1.382 0.869 1.861 1.707DETA 35.076 34.162 23.951 32.591 36.463 29.869 26.799AEEA 0.000 0.000 0.254 1.603 1.807 0.455 0.394AEP 2.193 2.794 3.951 1.914 1.135 3.122 2.893HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.772 3.324 1.853 2.782 2.789 2.443 2.4341-TETA 17.464 21.229 13.658 16.596 14.933 15.761 14.689DAEP 1.240 1.560 2.447 0.995 0.521 1.740 1.700PEEDA 0.891 1.074 0.289 0.699 0.388 0.125 0.247DPE 0.000 0.000 0.355 0.262 0.143 0.157 0.291AE-TAEA 4.199 5.092 0.220 4.454 4.587 4.487 4.7431-TEPA 9.456 11.417 10.338 9.746 8.931 11.169 10.912AE-DAEP 0.765 0.809 0.324 0.167 0.134 0.189 0.259AE-PEEDA 0.060 0.064 0.193 0.141 0.097 0.112 0.175iAE-PEEDA 0.278 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.242 0.496 0.187 0.158 0.174 0.433BPEA 0.000 0.000 0.734 0.667 0.692 0.754 0.232Others 6.124 6.280 20.326 8.645 7.394 10.911 15.928MEA conversion, % 90.76 95.12 97.45 85.78 74.59 95.86 97.37DETA conversion, % 41.33 47.41 60.62 47.66 41.42 51.33 56.29Acyclic(N4), wt. % 90.47 90.31 83.39 90.83 94.39 90.00 88.44Acyclic(N5), wt. % 92.53 93.67 85.81 92.43 92.59 92.72 93.44.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.66 0.65 0.66 0.72 0.78 0.83 0.87Acyclic(N4)/cyclic(<=N4), 3.63 3.62 1.69 3.69 5.80 2.60 2.50weight ratio__________________________________________________________________________
TABLE IX__________________________________________________________________________ Example No. 99 100 101 102 103 104 105 106__________________________________________________________________________Catalyst Type I I I I I I I ICatalyst weight, gm 78.44 78.44 78.44 78.44 78.44 78.44 78.44 78.44Pressure, psig 598 598 598 598 598 598 598 598Temperature, .degree.C. 268.2 270 280 258 268 270 279.6 269.3Time on organics, hrs. 24 4 29 48 53 72 77 96.25Duration of run, hrs. 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 2.38 3.12 3.09 3.01 3.06 2.97 2.39 3.07DETA/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 1.113 0.976 1.860 0.782 1.043 1.302 1.824 0.980MEA 10.615 12.327 5.220 14.139 10.320 9.098 6.092 8.653PIP 1.129 1.005 1.496 0.859 1.132 1.320 1.611 1.111DETA 36.799 37.931 31.746 39.773 37.334 36.528 34.990 34.182AEEA 1.033 1.258 0.344 1.844 1.311 1.136 0.541 1.124AEP 1.305 1.132 2.067 0.979 1.353 1.472 2.104 1.379HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.615 2.470 2.365 2.433 2.657 2.733 2.577 2.6121-TETA 14.292 13.515 14.587 14.440 14.597 14.582 14.930 13.465DAEP 0.594 0.489 1.269 0.296 0.595 0.603 1.041 0.647PEEDA 0.435 0.400 0.866 0.242 0.463 0.496 0.064 0.168DPE 0.131 0.135 0.159 0.052 0.133 0.092 0.091 0.150AE-TAEA 3.929 3.799 4.211 3.918 4.621 4.393 4.377 4.3571-TEPA 8.291 7.823 9.865 6.776 8.516 8.862 9.611 8.767AE-DAEP 0.503 0.527 1.032 0.400 0.502 0.089 0.121 0.177AE-PEEDA 0.099 0.115 0.175 0.082 0.088 0.060 0.083 0.122iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.163 0.228 0.356 0.253 0.153 0.091 0.117 0.297BPEA 0.610 0.599 0.845 0.412 0.618 0.748 0.798 0.729Others 7.223 7.030 12.137 4.048 6.784 6.715 8.479 10.461MEA conversion, % 71.04 66.53 86.00 61.31 72.29 75.11 83.32 76.14DETA conversion, % 40.33 38.80 49.40 35.32 40.42 40.60 43.06 43.99Acyclic(N4), wt. % 93.58 93.98 88.08 96.62 93.54 93.56 93.61 94.34Acyclic(N5), wt. % 89.89 88.77 85.39 90.32 90.62 93.07 92.60 90.83.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.75 0.77 0.86 0.68 0.79 0.77 0.81 0.85Acyclic(N4)/cyclic(< = N4), 4.70 5.06 2.89 6.95 4.69 4.35 3.57 4.66weight ratio__________________________________________________________________________
TABLE X__________________________________________________________________________ Example No. 107 108 109 110 111 112 113 114 115__________________________________________________________________________Catalyst Type J J J J J J J J JCatalyst weight, gm 73.3 73.3 73.3 73.3 73.3 73.3 73.3 73.3 73.3Pressure, psig 598 603 603 605 604 604.9 604 604 604Temperature, .degree.C. 274.8 274.2 280.3 261.2 271.4 261.8 180.2 269.7 269.6Time on organics, hrs. 6 8 26 33 50 54.5 74 98.5 100Duration of run, hrs. 2 2 2 2 2 2 2 1.5 1.5MEA SV, gmol/hr/kgcat 4.27 4.14 3.79 3.77 3.97 3.92 3.80 4.20 4.17DETA/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 1.429 1.424 3.172 0.868 1.570 0.800 3.025 0.882 1.051MEA 14.429 13.943 9.322 21.725 13.285 20.998 6.949 13.400 14.889PIP 1.355 1.300 2.261 0.868 1.478 0.814 2.234 1.030 1.176DETA 47.230 42.295 39.568 53.087 43.212 52.672 42.607 43.225 47.069AEEA 0.550 0.512 0.197 1.245 0.599 1.274 0.098 0.676 0.823AEP 1.672 1.513 2.379 0.784 1.629 0.825 2.731 1.328 1.396HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.605 2.279 2.424 2.158 2.317 2.279 2.342 2.467 2.7391-TETA 13.001 12.670 12.814 9.683 12.889 10.389 12.621 13.828 13.069DAEP 0.431 0.360 0.995 0.154 0.368 0.187 1.128 0.319 0.360PEEDA 0.302 0.232 0.710 0.092 0.242 0.106 0.753 0.216 0.238DPE 0.000 0.000 0.075 0.000 0.000 0.000 0.089 0.000 0.000AE-TAEA 2.986 2.963 3.398 1.553 2.893 1.804 3.351 3.239 3.0921-TEPA 5.571 5.909 7.347 2.674 5.827 3.180 7.449 6.276 6.252AE-DAEP 0.181 0.442 0.599 0.000 0.449 0.000 0.673 0.454 0.145AE-PEEDA 0.000 0.529 0.187 0.000 0.476 0.000 0.202 0.384 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.352 0.757 0.645 0.089 0.811 0.084 0.585 0.601 0.363BPEA 0.223 0.550 0.560 0.093 0.574 0.076 0.109 0.674 0.300Others 1.202 3.012 3.419 0.547 3.170 0.521 3.655 3.060 1.300MEA conversion, % 61.11 61.45 74.39 42.37 63.75 43.71 81.09 63.56 60.17DETA conversion, % 24.34 30.49 35.40 14.85 29.93 16.08 31.11 30.14 25.17Acyclic(N4), wt. % 95.51 96.19 89.54 97.97 96.15 97.74 88.37 96.82 96.36Acyclic(N5), wt. % 91.88 79.57 84.37 95.88 79.06 96.89 87.32 81.83 92.04.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.57 0.72 0.75 0.36 0.70 0.40 0.73 0.69 0.62Acyclic(N4)/cyclic(< = N4), 4.15 4.39 2.37 6.24 4.09 6.56 2.16 5.63 4.99weight ratio__________________________________________________________________________
TABLE XI__________________________________________________________________________ Example No. 116 117 118 119 120 121 122 123 124__________________________________________________________________________Catalyst Type K K K K K K K K KCatalyst weight, gm 78.4 78.4 78.4 78.4 78.4 78.4 78.4 78.4 78.4Pressure, 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 52 71 76 95 100 120Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.21 3.22 3.15 3.26 3.16 3.28 2.60 3.20 2.85DETA/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 2.011 1.726 3.400 1.045 1.704 2.927 2.694 1.875 2.016MEA 19.645 19.830 10.922 24.936 17.747 13.549 6.399 19.549 17.740PIP 1.597 1.489 2.412 0.797 1.531 2.082 2.206 1.710 1.570DETA 49.999 49.815 44.929 54.559 49.660 43.523 37.413 49.063 49.599AEEA 0.269 0.305 0.156 0.448 0.288 0.213 0.000 0.288 0.481AEP 1.525 1.493 2.688 0.754 1.573 3.273 2.897 1.565 1.777HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.104 2.144 2.134 1.661 2.231 4.370 1.861 2.034 2.0611-TETA 9.952 10.859 11.222 7.684 10.454 11.481 11.542 9.840 10.021DAEP 0.081 0.238 1.038 0.095 0.470 1.096 1.664 0.680 0.442PEEDA 0.215 0.153 0.603 0.062 0.241 0.388 1.166 0.368 0.000DPE 0.000 0.000 0.051 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 0.000 0.000 0.000 0.000 0.000 4.286 4.233 0.000 1.8831-TEPA 1.592 1.629 2.342 0.742 1.760 4.935 8.341 1.975 2.969AE-DAEP 0.000 0.168 0.443 0.077 0.178 0.160 1.448 0.296 0.000AE-PEEDA 0.160 0.000 0.095 0.000 0.069 0.000 0.614 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.066 0.073 0.204 0.051 0.268 0.089 0.503 0.000 0.000BPEA 0.000 0.000 0.076 0.000 0.000 0.000 0.496 0.000 0.000Others 3.564 3.489 6.276 2.170 3.688 1.449 6.241 2.737 0.000MEA conversion, % 45.57 45.47 69.23 31.62 50.63 63.79 82.59 45.48 49.85DETA conversion, % 17.68 18.59 24.77 11.08 17.90 30.86 39.50 18.68 16.68Acyclic(N4), wt. % 97.60 97.08 88.75 98.34 94.69 91.44 82.57 91.89 96.47Acyclic(N5), wt. % 87.57 87.12 74.10 85.31 77.39 97.37 80.42 86.95 100.00.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.15 0.14 0.21 0.09 0.17 0.55 0.96 0.18 0.39Acyclic(N4)/cyclic(< = N4), 3.53 3.86 1.97 5.47 3.33 2.32 1.69 2.75 3.19weight ratio__________________________________________________________________________
TABLE XII__________________________________________________________________________ Example No. 125 126 127 128 129 130 131 132 133__________________________________________________________________________Catalyst Type L L L L L L L L LCatalyst weight, gm 73.2 73.2 73.2 73.2 73.2 73.2 73.2 73.2 73.2Pressure, 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 7.5 26.5 31.5 49.75 54 74 77.5 80Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.58 4.67 4.05 4.77 4.61 4.82 4.51 4.47 4.60DETA/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 0.979 1.000 2.216 0.524 0.877 0.472 2.124 1.229 1.025MEA 17.990 19.335 10.087 24.701 17.662 24.119 9.596 17.400 17.389PIP 0.989 0.964 1.718 0.593 0.993 0.590 1.696 1.203 1.145DETA 50.172 53.162 45.219 55.645 50.697 55.944 45.259 49.313 51.748AEEA 0.000 0.433 0.000 1.012 0.642 1.026 0.126 0.667 0.713AEP 1.134 1.062 2.216 0.613 1.091 0.648 2.172 1.229 1.334HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.208 2.198 2.406 1.617 2.175 1.619 2.323 2.162 2.3071-TETA 9.955 10.785 12.776 7.737 10.803 7.844 12.734 10.465 11.340DAEP 0.232 0.218 0.936 0.103 0.249 0.110 0.896 0.273 0.300PEEDA 0.124 0.143 0.603 0.062 0.166 0.000 0.576 0.174 0.184DPE 0.000 0.075 0.075 0.000 0.000 0.000 0.085 0.000 0.000AE-TAEA 1.588 1.180 3.177 0.735 2.054 0.826 3.277 1.942 2.2551-TEPA 2.656 2.775 6.758 1.190 3.841 1.534 6.807 4.191 4.651AE-DAEP 0.114 0.097 0.606 0.000 0.000 0.000 0.525 0.086 0.106AE-PEEDA 0.000 0.000 0.149 0.000 0.000 0.000 0.136 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 0.235 0.000 0.000 0.000 0.222 0.121 0.135BPEA 0.000 0.000 0.112 0.000 0.000 0.000 0.109 0.100 0.128Others 6.460 0.646 1.993 0.269 0.439 0.218 1.489 0.694 0.701MEA conversion, % 52.45 47.17 72.49 32.06 50.75 33.87 73.52 51.33 53.62DETA conversion, % 19.53 13.67 26.69 9.04 15.98 8.83 25.77 18.02 17.97Acyclic(N4), wt. % 97.15 97.30 90.39 98.27 96.90 98.85 90.62 96.58 96.57Acyclic(N5), wt. % 97.38 97.61 90.01 100.00 100.00 100.00 91.03 95.24 94.93.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.35 0.30 0.66 0.20 0.44 0.25 0.67 0.49 0.51Acyclic(N4)/cyclic(< = N4), 4.91 5.44 2.74 6.83 5.19 7.02 2.78 4.39 4.61weight ratio__________________________________________________________________________
TABLE XIII__________________________________________________________________________ Example No. 134 135 136 137 138 139 140 141 142__________________________________________________________________________Catalyst Type M M M M M M M M MCatalyst weight, gm 76.6 76.6 76.6 76.6 76.6 76.6 76.6 76.6 76.6Pressure, psig 597 599 594 596 597 598 598 578 592Temperature, .degree.C. 274.8 274.2 280.3 261.2 271.4 261.8 280.2 269.7 269.6Time on organics, hrs. 6 8 26 33 50 54.5 74 98.5 100Duration of run, hrs. 2 2 2 2 2 2 2 1.5 1.5MEA SV, gmol/hr/kgcat 3.47 3.41 3.15 3.08 3.28 3.12 3.05 3.41 3.47DETA/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 2.061 2.011 3.148 1.184 2.307 1.307 3.298 4.426 1.702MEA 11.521 11.310 6.396 20.282 13.265 20.615 5.659 11.296 14.677PIP 1.527 1.470 2.157 0.932 1.702 0.989 2.146 3.452 1.419DETA 42.334 40.741 38.310 49.435 42.179 50.484 37.713 34.699 46.940AEEA 0.171 0.229 0.345 1.161 0.498 1.159 0.000 0.094 0.619AEP 2.239 2.094 3.230 0.922 1.874 0.956 3.141 5.456 1.744HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.485 2.769 2.228 2.289 2.411 2.243 1.952 1.031 2.4731-TETA 13.469 14.759 13.494 11.956 12.180 10.324 11.730 8.626 13.276DAEP 0.942 0.959 1.643 0.249 0.703 0.219 1.537 2.523 0.455PEEDA 0.758 0.783 1.241 0.150 0.500 0.132 1.082 1.975 0.332DPE 0.099 0.097 0.135 0.000 0.076 0.000 0.130 0.128 0.000AE-TAEA 3.476 3.863 3.743 2.042 3.220 1.844 3.286 1.977 3.0251-TEPA 6.876 7.762 8.263 3.497 6.138 3.258 7.403 4.058 5.508AE-DAEP 0.571 0.509 1.049 0.000 0.355 0.000 1.086 2.356 0.367AE-PEEDA 0.150 0.159 0.419 0.000 0.107 0.000 0.878 0.928 0.121iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.410 0.460 0.567 0.176 0.433 0.123 0.974 0.089 0.242BPEA 0.370 0.402 0.445 0.148 0.335 0.123 0.797 0.129 0.142Others 3.222 3.202 4.458 0.022 2.377 0.934 5.999 8.878 1.378MEA conversion, % 69.06 69.99 82.87 44.85 63.31 44.03 84.47 69.87 60.81DETA conversion, % 32.44 35.75 39.01 20.11 30.67 18.54 38.47 45.00 25.51Acyclic(N4), wt. % 89.87 90.50 83.90 97.28 91.94 97.28 83.27 67.62 95.24Acyclic(N5), wt. % 87.34 88.37 82.89 94.47 88.39 95.40 74.10 63.28 90.73.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.67 0.68 0.77 0.40 0.67 0.41 0.88 0.67 0.57Acyclic(N4)/cyclic(< = N4), 2.87 3.24 1.87 6.32 3.01 5.47 1.70 0.71 3.99weight ratio__________________________________________________________________________
TABLE XIV__________________________________________________________________________ Example No. 143 144 145 146 147 148 149 150 151__________________________________________________________________________Catalyst Type N N N N N N N N NCatalyst weight, gm 77.2 77.2 77.2 77.2 77.2 77.2 77.2 77.2 77.2Pressure, psig 606 602 603 599 605 601.3 604 605 602Temperature, .degree.C. 274.8 274.2 280.3 261.2 271.4 261.8 280.2 269.7 269.6Time on organics, hrs. 6 8 26 33 50 54.5 74 98.5 100Duration of run, hrs. 2 2 2 2 2 2 2 1.5 1.5MEA SV, gmol/hr/kgcat 3.66 3.28 3.32 3.12 3.38 3.23 3.28 3.68 3.71DETA/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 4.605 3.886 5.431 1.582 3.133 1.518 5.888 2.090 2.159MEA 14.165 13.840 8.988 20.796 15.163 22.247 9.341 16.165 15.935PIP 2.743 2.486 3.003 1.044 1.960 1.001 3.051 1.333 1.433DETA 39.645 39.381 34.406 46.873 40.571 50.785 37.693 42.241 45.956AEEA 0.101 0.264 0.101 0.891 0.476 0.962 0.000 0.631 0.594AEP 3.421 3.180 4.196 1.218 2.294 1.114 3.834 1.851 1.880HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.671 1.753 1.198 1.910 2.183 2.023 1.193 2.292 2.4591-TETA 10.517 11.090 10.855 9.315 11.704 9.626 10.401 11.963 12.528DAEP 1.223 1.224 1.875 0.287 0.898 0.251 1.503 0.631 0.765PEEDA 1.151 1.136 1.743 0.206 0.759 0.177 1.167 0.451 0.617DPE 0.130 0.119 0.213 0.000 0.080 0.000 0.109 0.000 0.105AE-TAEA 2.230 2.468 2.555 1.718 2.775 1.629 2.507 2.873 3.1831-TEPA 5.038 5.654 6.324 3.175 5.413 2.702 5.290 5.112 5.477AE-DAEP 0.832 0.808 1.544 0.156 0.488 0.107 1.070 0.396 0.424AE-PEEDA 0.403 0.315 0.858 0.000 0.160 0.000 0.446 0.111 0.106iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.130 0.259 0.457 0.096 0.092 0.000 0.307 0.366 0.235BPEA 0.134 0.409 0.354 0.122 0.279 0.000 0.451 0.213 0.175Others 4.461 4.200 9.270 1.000 3.341 0.756 6.468 2.101 1.798MEA conversion, % 61.68 62.60 76.38 40.76 58.41 39.45 74.52 57.13 58.04DETA conversion, % 36.26 36.76 46.26 20.64 33.86 17.85 38.88 26.66 28.09Acyclic(N4), wt. % 82.96 83.82 75.88 95.80 88.88 96.46 80.67 92.94 90.97Acyclic(N5), wt. % 82.90 81.94 73.43 92.89 88.93 97.60 77.42 88.03 90.21.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.60 0.65 0.76 0.45 0.59 0.37 0.70 0.59 0.58Acyclic(N4)/cyclic(< = N4), 1.41 1.58 1.09 4.07 2.32 4.58 1.20 3.34 3.12weight ratio__________________________________________________________________________
TABLE XV__________________________________________________________________________ Example No. 152 153 154 155 156 157 158 159 160__________________________________________________________________________Catalyst Type O O O O O O O O OCatalyst weight, gm 74.1 74.1 74.1 74.1 74.1 74.1 74.1 74.1 74.1Pressure, 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 7.5 26.5 31.5 49.75 54 74 77.5 80Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.32 4.45 3.86 4.75 4.55 4.76 4.72 4.88 4.68DETA/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 0.799 0.893 2.371 0.614 1.122 0.619 1.998 0.866 1.017MEA 16.923 18.142 8.959 23.814 16.116 25.054 10.110 16.161 17.198PIP 1.117 1.135 0.000 0.764 1.371 0.835 1.977 1.209 1.356DETA 50.969 52.494 43.962 55.309 48.689 54.390 47.265 50.840 51.369AEEA 0.000 0.655 0.113 1.240 0.695 1.219 0.126 0.812 0.802AEP 1.445 1.273 2.405 0.656 1.488 0.655 2.444 1.326 1.362HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.361 2.414 2.424 1.705 2.211 1.553 2.474 2.443 2.3191-TETA 10.806 11.071 12.003 8.100 10.604 7.390 12.128 11.857 11.027DAEP 0.223 0.211 1.034 0.102 0.328 0.101 0.788 0.287 0.268PEEDA 0.000 0.150 0.742 0.000 0.209 0.000 0.537 0.199 0.180DPE 0.000 0.000 0.122 0.000 0.000 0.000 0.109 0.000 0.000AE-TAEA 1.975 1.711 2.755 0.748 2.130 0.714 2.508 2.424 1.8701-TEPA 3.599 3.260 6.223 1.444 4.940 1.373 5.742 5.006 3.901AE-DAEP 0.249 0.000 0.609 0.000 0.099 0.000 0.378 0.000 0.000AE-PEEDA 0.508 0.000 0.659 0.000 0.000 0.000 0.116 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.236 0.000 0.800 0.000 0.118 0.000 0.334 0.140 0.099BPEA 0.164 0.000 0.533 0.000 0.126 0.000 0.204 0.121 0.116Others 2.605 0.440 4.535 0.205 0.635 0.218 1.962 0.607 0.694MEA conversion, % 54.25 50.54 75.37 34.57 54.94 30.55 72.30 56.49 53.15DETA conversion, % 18.10 14.95 28.17 9.69 19.10 10.39 23.03 18.65 16.84Acyclic(N4), wt. % 98.33 97.39 88.38 98.97 95.98 98.88 91.06 96.71 96.75Acyclic(N5), wt. % 82.81 100.00 77.54 100.00 95.38 100.00 88.88 96.60 96.42.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.50 0.36 0.71 0.22 0.56 0.23 0.58 0.52 0.43Acyclic(N4)/cyclic(< = N4), 4.73 4.87 3.35 6.44 3.77 5.62 2.58 4.73 4.21weight ratio__________________________________________________________________________
TABLE XVI__________________________________________________________________________ Example No. 161 162 163 164 165 166 167 168 169__________________________________________________________________________Catalyst Type P P P P P P P P PCatalyst weight, gm 78.9 78.9 78.9 78.9 78.9 78.9 78.9 78.9 78.9Pressure, 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 7 26 31 50 55 74 79 99.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.12 3.22 3.28 3.33 3.43 3.59 3.37 3.31 3.46DETA/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 1.169 1.189 2.230 1.402 1.099 0.671 1.752 0.918 1.448MEA 15.817 15.231 6.402 28.485 16.384 22.977 5.783 12.331 15.301PIP 1.664 1.609 2.315 1.465 1.764 1.139 2.015 1.420 1.843DETA 52.256 51.487 43.212 53.634 51.751 53.055 43.336 47.964 50.154AEEA 0.283 0.283 0.000 1.094 0.153 0.886 0.000 0.400 0.339AEP 1.915 1.855 2.978 0.777 1.978 1.094 2.884 1.762 2.059HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.062 2.339 1.830 0.884 2.131 1.899 2.473 2.651 2.2591-TETA 11.022 11.780 12.001 6.150 11.397 9.186 13.960 13.405 11.464DAEP 0.337 0.328 1.290 0.078 0.299 0.126 1.238 0.389 0.381PEEDA 0.207 0.217 0.927 0.046 0.186 0.076 0.763 0.288 0.260DPE 0.000 0.000 0.251 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 1.815 1.985 2.926 0.503 1.572 1.100 3.768 3.096 1.8801-TEPA 3.691 3.831 7.181 0.912 3.369 2.347 8.080 6.384 3.990AE-DAEP 0.243 0.116 1.511 0.121 0.213 0.276 0.809 0.295 0.138AE-PEEDA 0.000 0.000 0.928 0.000 0.000 0.000 0.238 0.136 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 1.302 0.000 0.106 0.156 0.212 0.000 0.537BPEA 0.000 0.000 0.709 0.000 0.000 0.000 0.505 0.127 0.377Others 0.459 0.872 2.746 0.399 0.607 0.361 2.423 0.974 1.252MEA conversion, % 56.77 58.52 82.77 22.06 55.23 37.72 84.29 66.57 58.72DETA conversion, % 15.12 16.67 30.89 12.79 15.96 14.53 30.04 22.72 19.59Acyclic(N4), wt. % 96.01 96.29 84.86 98.26 96.54 98.20 89.14 95.95 95.54Acyclic(N5), wt. % 95.76 98.04 69.43 92.12 93.94 88.86 87.04 94.45 84.81.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.42 0.40 0.89 0.21 0.38 0.34 0.74 0.60 0.48Acyclic(N4)/cyclic(< = N4), 3.17 3.52 1.78 2.97 3.20 4.55 2.38 4.16 3.02weight ratio__________________________________________________________________________
TABLE XVII__________________________________________________________________________ Example No. 170 171 172 173 174 175 176 177 178__________________________________________________________________________Catalyst Type Q Q Q Q Q Q Q Q QCatalyst weight, gm 75 75 75 75 75 75 75 75 75Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 271.8 270 280.2 260.9 270.6 261.2 281.5 270 270Time on organics, hrs. 5 8.5 25 30 34 49 55 76 78Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.47 4.56 4.56 4.83 4.82 4.39 4.36 4.29 4.45DETA/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 0.810 0.695 1.728 0.496 1.051 0.606 2.250 1.081 1.235MEA 17.286 19.405 12.726 23.941 20.602 23.930 10.050 16.058 17.476PIP 0.000 0.893 1.726 0.691 1.246 0.771 1.912 1.336 1.440DETA 49.596 50.668 47.269 55.529 51.649 54.615 43.590 49.568 50.015AEEA 0.486 0.691 0.138 1.063 0.715 1.234 0.241 0.655 0.684AEP 1.371 0.938 1.974 0.669 1.231 0.731 2.221 1.449 1.413HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.260 2.121 2.389 1.786 2.157 1.878 2.470 2.355 2.1871-TETA 12.072 9.647 11.834 8.149 10.098 8.642 12.086 11.364 11.254DAEP 0.252 0.179 0.649 0.097 0.211 0.112 0.851 0.313 0.251PEEDA 0.179 0.124 0.372 0.070 0.144 0.071 0.630 0.209 0.172DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.068 0.000 0.000AE-TAEA 2.502 1.504 2.751 0.826 1.555 0.937 2.780 2.257 2.0151-TEPA 4.580 2.966 5.577 1.450 2.954 1.689 6.099 4.795 4.114AE-DAEP 0.259 0.000 0.387 0.000 0.084 0.000 0.395 0.000 0.231AE-PEEDA 0.105 0.000 0.100 0.000 0.000 0.000 0.111 0.000 0.177iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.166 0.000 1.181 0.000 0.077 0.000 0.451 0.115 0.108BPEA 0.000 0.068 0.138 0.000 0.100 0.000 0.352 0.164 0.105Others 0.756 0.599 1.252 0.294 0.726 0.304 2.563 0.790 0.884MEA conversion, % 52.45 44.86 64.94 34.49 44.04 34.90 71.93 55.92 52.53DETA conversion, % 18.91 14.44 22.61 9.70 16.62 11.71 27.65 19.14 19.26Acyclic(N4), wt. % 97.08 97.48 93.30 98.35 97.19 98.29 90.39 96.33 96.95Acyclic(N5), wt. % 93.03 98.50 91.18 100.00 94.52 100.00 87.15 96.19 90.81.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.52 0.38 0.60 0.23 0.38 0.25 0.63 0.51 0.49Acyclic(N4)/cyclic(< = N4), 7.95 5.51 3.01 6.51 4.33 6.24 2.56 4.15 4.10weight ratio__________________________________________________________________________
TABLE XVIII__________________________________________________________________________ Example No. 179 180 181 182 183 184 185 186 187__________________________________________________________________________Catalyst Type R R R R R R R R RCatalyst weight, gm 74.9 74.9 74.9 74.9 74.9 74.9 74.9 74.9 74.9Pressure, 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 52 71 76 95 100 120Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.93 3.73 3.63 3.84 3.64 3.67 3.53 3.56 3.35DETA/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 0.980 0.906 2.141 0.568 1.040 0.888 2.069 1.289 1.356MEA 20.085 19.419 12.916 27.282 20.217 25.518 12.998 22.393 20.330PIP 1.509 1.448 2.211 0.850 1.624 0.922 2.027 1.573 1.718DETA 52.434 51.557 46.545 55.689 52.087 54.254 47.895 52.707 52.473AEEA 0.262 0.255 0.178 0.429 0.220 0.421 0.000 0.268 0.263AEP 1.402 1.413 2.106 0.696 1.428 0.823 2.307 1.348 1.537HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.988 2.084 2.094 1.374 1.867 1.680 1.920 1.733 1.9441-TETA 9.493 9.950 10.311 6.413 8.947 7.890 9.728 7.823 8.760DAEP 0.173 0.198 0.645 0.058 0.382 0.275 0.714 0.279 0.373PEEDA 0.127 0.146 0.460 0.052 0.150 0.192 0.328 0.000 0.000DPE 0.000 0.000 0.056 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.0001-TEPA 1.257 1.371 2.257 0.448 1.195 0.801 2.316 0.979 1.375AE-DAEP 0.000 0.292 0.334 0.000 0.091 0.104 0.624 0.000 0.000AE-PEEDA 0.084 0.135 0.070 0.000 0.000 0.000 0.485 0.000 0.000iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.208 0.779 1.181 0.000 0.365 0.281 0.490 0.000 0.365BPEA 0.000 0.000 0.287 0.000 0.000 0.000 0.631 0.000 0.000Others 2.920 3.097 5.689 1.582 2.587 1.652 6.070 1.507 2.305MEA conversion, % 44.42 46.57 63.21 25.08 43.62 30.56 63.95 36.84 43.63DETA conversion, % 13.76 15.69 21.21 9.11 13.68 12.26 21.06 11.65 13.54Acyclic(N4), wt. % 97.46 97.22 91.45 98.61 95.31 95.35 91.79 97.16 96.64Acyclic(N5), wt. % 81.13 53.17 72.13 100.00 72.41 67.51 50.94 100.00 79.03.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.13 0.21 0.23 0.06 0.15 0.12 0.36 0.10 0.16Acyclic(N4)/cyclic(< = N4), 3.58 3.76 2.26 4.70 3.02 4.33 2.17 2.99 2.95weight ratio__________________________________________________________________________
TABLE XIX__________________________________________________________________________ Example No. 188 189 190 191 192 193 194 195 196__________________________________________________________________________Catalyst Type S S S S S S S S SCatalyst weight, gm 77.1 77.1 77.1 77.1 77.1 77.1 77.1 77.1 77.1Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 270.3 270.8 280.9 259.5 270.8 261.4 282.6 272.4 270.8Time on organics, hrs. 4 7 26 31 50 55 74 79 99.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.57 3.84 3.80 3.90 4.07 4.29 4.00 4.02 4.09DETA/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 1.064 1.067 2.949 1.044 1.126 0.634 1.319 0.655 0.856MEA 19.737 20.664 15.833 33.488 22.772 28.699 10.428 16.261 18.470PIP 1.010 1.060 2.508 1.029 1.433 0.868 1.591 0.964 1.166DETA 52.528 52.478 47.832 54.061 52.460 55.001 46.963 50.475 53.782AEEA 0.618 0.649 0.219 0.981 0.066 1.055 0.134 0.751 0.219AEP 1.111 1.092 2.117 0.537 1.255 0.600 2.045 1.283 1.400HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.982 1.964 1.306 0.527 1.836 1.309 2.590 2.505 2.0821-TETA 10.911 10.012 8.857 4.302 9.388 6.368 13.545 12.661 10.355DAEP 0.183 0.172 0.652 0.031 0.165 0.065 0.739 0.233 0.193PEEDA 0.134 0.122 0.487 0.000 0.108 0.000 0.478 0.186 0.154DPE 0.000 0.000 0.321 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 1.065 1.592 1.529 0.149 0.830 0.433 3.290 2.387 1.4781-TEPA 2.728 3.034 2.962 0.125 2.166 0.748 6.467 4.760 2.918AE-DAEP 0.123 0.000 0.376 0.000 0.049 0.125 0.366 0.110 0.086AE-PEEDA 0.000 0.000 0.218 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 0.142 0.198 0.600 0.000 0.000 0.000 0.151 0.105 0.000BPEA 0.000 0.000 0.310 0.000 0.000 0.000 0.157 0.065 0.000Others 0.983 0.675 2.785 0.347 1.245 0.414 1.358 0.510 1.052MEA conversion, % 46.25 43.91 56.39 7.91 37.98 21.73 71.61 56.02 49.81DETA conversion, % 14.98 15.34 21.70 11.65 15.09 10.85 24.02 18.86 13.13Acyclic(N4), wt. % 97.60 97.60 87.44 99.35 97.63 99.16 92.99 97.31 97.29Acyclic(N5), wt. % 93.48 95.89 74.91 100.00 98.39 90.46 93.53 96.24 98.09.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.31 0.39 0.52 0.06 0.26 0.17 0.60 0.48 0.35Acyclic(N4)/cyclic(< = N4), 5.29 4.89 1.67 3.02 3.79 5.01 3.32 5.69 4.27weight ratio__________________________________________________________________________
TABLE XX__________________________________________________________________________ Example No. 197 198 199 200 201 202 203 204 205__________________________________________________________________________Catalyst Type T T T T T T T T TCatalyst weight, gm 89.1 89.1 89.1 89.1 89.1 89.1 89.1 89.1 89.1Pressure, 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 26 45.5 50.5 69 74.5 95 119 120Duration of run, hrs. 2 2 2 2 2 2 2 1 1MEA SV, gmol/hr/kgcat 3.54 3.49 3.26 3.62 3.67 3.54 3.50 7.34 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 2.720 2.147 6.050 1.506 2.063 0.510 4.522 1.700 1.717MEA 17.172 17.646 11.090 24.376 18.880 23.711 12.670 19.091 19.532PIP 3.605 3.285 6.865 1.922 2.983 1.500 5.411 2.536 2.650DETA 45.019 47.846 36.936 51.126 46.069 60.718 38.319 46.051 46.810AEEA 1.105 0.896 0.266 2.671 1.310 1.103 0.484 1.774 1.241AEP 2.925 2.891 6.159 1.195 2.402 1.058 4.968 2.089 2.120HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.209 0.424 0.376 0.813 1.233 0.599 0.517 1.195 0.7821-TETA 10.239 10.478 8.946 8.826 10.269 6.805 9.581 9.683 9.534DAEP 0.772 0.760 1.868 0.178 0.640 0.127 1.531 0.559 0.548PEEDA 0.840 0.880 2.576 0.170 0.724 0.140 2.159 0.624 0.603DPE 0.041 0.054 0.072 0.000 0.086 0.000 0.101 0.052 0.032AE-TAEA 0.934 0.596 0.549 0.231 0.979 0.000 0.711 0.904 0.7881-TEPA 4.738 4.381 4.535 2.107 4.687 0.000 5.357 4.353 4.151AE-DAEP 0.398 0.278 1.152 0.049 0.262 0.000 0.969 0.257 0.237AE-PEEDA 0.126 0.129 0.254 0.000 0.115 0.000 0.235 0.109 0.104iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.047 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 1.657 1.439 3.878 0.448 1.598 0.000 3.154 1.704 1.370MEA Conversion, % 53.55 52.50 70.19 33.82 49.12 35.88 65.36 47.50 45.94DETA Conversion, % 27.63 23.46 41.00 17.51 26.21 2.41 37.74 24.74 23.00Acyclic(N4), wt. % 87.38 86.56 67.36 96.51 88.80 96.51 72.70 89.80 89.71Acyclic(N5), wt. % 91.53 92.44 77.77 97.93 93.75 0.00 83.44 93.50 93.54.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.47 0.43 0.47 0.24 0.47 0.00 0.52 0.46 0.46Acyclic(N4)/cyclic(< = N4), 1.40 1.39 0.53 2.78 1.68 2.61 0.71 1.86 1.73weight ratio__________________________________________________________________________
TABLE XXI__________________________________________________________________________ Example No. 206 207 208 209 210 211 212 213 214__________________________________________________________________________Catalyst Type U U U U U U U U UCatalyst weight, gm 91.7 91.7 91.7 91.7 91.7 91.7 91.7 91.7 91.7Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 268.6 268.9 278.6 259.1 268.3 258.2 278.9 269 269.6Time on organics, hrs. 3 22 27 51 69.5 74 93 99 116.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 1.87 2.59 2.79 2.74 2.82 2.85 2.58 2.74 2.59DETA/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 2.183 2.188 1.770 0.548 1.020 0.597 1.940 1.065 1.184MEA 27.641 27.702 4.345 16.309 9.520 16.119 3.529 9.960 7.884PIP 0.359 0.359 1.724 0.781 1.295 0.831 1.768 1.334 1.404DETA 50.123 50.233 32.473 45.537 37.563 44.839 30.507 38.688 35.307AEEA 1.469 1.473 0.272 2.441 0.835 2.461 0.259 0.891 0.693AEP 0.425 0.425 2.604 0.939 1.587 0.990 2.516 1.641 1.764HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.540 0.541 1.884 1.758 2.057 1.894 1.864 1.979 2.0251-TETA 5.907 5.920 14.212 13.575 13.856 13.962 13.839 13.903 13.810DAEP 0.000 0.000 1.323 0.221 0.725 0.221 1.371 0.816 0.894PEEDA 0.077 0.077 1.066 0.195 0.561 0.189 1.056 0.588 0.667DPE 0.000 0.000 0.212 0.073 0.453 0.073 0.204 0.194 0.226AE-TAEA 0.243 0.243 3.128 1.661 2.763 1.921 3.001 2.711 2.9541-TEPA 0.585 0.586 9.266 4.428 7.937 4.979 9.181 7.693 8.505AE-DAEP 0.000 0.000 1.117 0.186 0.635 0.255 1.174 0.589 0.748AE-PEEDA 0.151 0.152 0.266 0.147 0.165 0.151 0.247 0.180 0.234iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.000 0.000 0.400 0.000 0.339 0.241 0.370 0.292 0.377BPEA 0.000 0.000 0.692 0.194 0.581 0.058 0.692 0.473 0.620Others 1.677 1.680 14.327 2.888 11.047 4.339 13.830 8.942 12.375MEA Conversion, % 20.18 20.18 88.44 54.92 74.73 56.63 90.23 73.20 78.90DETA Conversion, % 13.97 13.97 48.67 25.19 40.75 28.30 49.82 38.12 43.84Acyclic(N4), % 98.82 98.82 86.09 96.91 90.15 97.10 85.65 90.86 89.86Acyclic(N5), % 84.54 84.54 83.35 92.03 86.15 90.74 83.07 87.15 85.28.SIGMA.(N5)/.SIGMA.(N4), 0.15 0.15 0.80 0.42 0.70 0.47 0.80 0.68 0.76weight ratioAcyclic(N4)/cyclic 7.50 7.50 2.32 6.94 3.44 6.91 2.27 3.47 3.20(< = N4), weight ratio__________________________________________________________________________
TABLE XXII__________________________________________________________________________ Example No. 215 216 217 218 219 220 221 222 223__________________________________________________________________________Catalyst Type V V V V V V V V VCatalyst weight, gm 79.6 79.6 79.6 79.6 79.6 79.6 79.6 79.6 79.6Pressure, psig 600 600 600 600 600 600 600 600 600Temperature, .degree.C. 268.6 268.9 278.6 259.1 268.3 258.2 278.9 269 269.6Time on organics, hrs. 3 22 27 51 69.5 74 93 99 116.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.34 2.66 2.48 3.46 3.32 3.85 2.73 2.84 2.42DETA/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 0.402 0.984 1.667 0.394 0.739 0.489 1.751 1.291 1.139MEA 15.275 9.355 3.835 17.705 9.833 17.982 3.544 9.828 6.948PIP 1.023 1.416 1.735 0.823 1.192 0.874 1.765 1.556 1.504DETA 45.636 38.050 30.599 46.962 37.022 46.771 30.103 39.458 33.830AEEA 0.563 0.635 0.229 2.288 0.818 2.437 0.237 0.909 0.647AEP 1.146 1.654 2.572 0.964 1.493 0.918 2.432 1.661 1.837HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.055 1.701 1.742 1.714 1.968 1.798 1.727 1.992 1.9651-TETA 14.353 14.398 14.401 12.742 14.026 12.801 13.949 14.704 14.368DAEP 0.249 0.654 1.412 0.204 0.702 0.176 1.305 0.678 0.917PEEDA 0.325 0.561 1.102 0.191 0.551 0.167 1.053 0.549 0.702DPE 0.121 0.297 0.229 0.068 0.281 0.065 0.214 0.195 0.339AE-TAEA 1.394 2.685 2.896 1.785 2.857 2.350 2.894 2.684 2.9501-TEPA 5.057 7.739 9.422 4.753 8.218 4.811 9.500 7.913 9.201AE-DAEP 0.509 0.622 1.153 0.165 0.574 0.183 1.120 0.446 0.733AE-PEEDA 0.114 0.112 0.260 0.085 0.186 0.082 0.318 0.112 0.220iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.157 0.184 0.396 0.088 0.450 0.068 0.417 0.000 0.374BPEA 0.332 0.572 0.676 0.225 0.581 0.214 0.673 0.443 0.631Others 4.749 7.940 13.943 2.415 10.748 2.214 13.837 6.329 12.335MEA Conversion, % 58.32 74.19 89.50 51.84 73.69 51.51 90.14 73.15 81.27DETA Conversion, % 26.00 37.61 50.21 24.08 41.13 25.04 50.22 35.93 45.79Acyclic(N4), % 95.68 91.41 85.48 96.90 91.24 97.28 85.90 92.15 89.29Acyclic(N5), % 85.30 87.49 83.21 92.07 86.08 92.90 83.07 91.37 86.12.SIGMA.(N5)/.SIGMA.(N4), 0.47 0.68 0.78 0.48 0.73 0.51 0.82 0.64 0.77weight ratioAcyclic(N4)/cyclic 5.38 3.51 2.29 6.43 3.79 6.63 2.32 3.60 3.08(< = N4), weight ratio__________________________________________________________________________
TABLE XXIII__________________________________________________________________________ Example No. 224 225 226 227 228 229 230 231 232 233__________________________________________________________________________Catalyst Type W W W W W W W W W WCatalyst weight, gm 87.7 87.7 87.7 87.7 87.7 87.7 87.7 87.7 87.7 87.7Pressure, psig 603 596 606 600 600 600 607 600 590 600Temperature, .degree.C. 269 279 260 270 270 259.6 279 270 280 270Time on organics, hrs. 21 28 49 54 73.5 97.5 116 121 139 144Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 0.91 0.59 2.75 1.43 2.59 2.77 2.41 2.60 2.29 2.43DETA/MEA mole ratio 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 5.97Crude product composition, wt. %EDA 2.350 1.919 0.622 0.752 0.640 0.391 1.122 0.738 1.310 1.032MEA 23.993 22.805 29.044 27.951 26.940 30.561 23.577 28.244 22.626 14.670PIP 0.625 0.683 0.215 0.276 0.295 0.203 0.700 0.146 0.834 1.073DETA 52.709 52.718 55.792 52.407 51.421 56.953 49.965 55.022 49.613 43.078AEEA 0.839 0.906 0.676 0.848 0.865 0.965 0.936 1.077 0.953 1.870AEP 0.670 0.712 0.316 0.322 0.328 0.257 0.586 0.387 0.639 1.002HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.188 1.399 0.875 0.858 0.973 0.696 1.543 1.161 1.716 2.4081-TETA 5.320 6.386 4.275 4.119 4.573 3.717 7.655 5.591 8.550 11.687DAEP 0.347 0.266 0.123 0.104 0.092 0.061 0.191 0.106 0.224 0.280PEEDA 0.057 0.170 0.083 0.060 0.058 0.038 0.023 0.067 0.028 0.239DPE 0.083 0.083 0.030 0.034 0.035 0.027 0.067 0.045 0.075 0.094AE-TAEA 0.899 0.988 0.607 0.509 0.572 0.374 0.052 0.789 1.664 3.0611-TEPA 1.485 1.792 1.076 0.867 0.939 0.666 2.604 1.419 3.031 5.965AE-DAEP 0.280 0.202 0.116 0.085 0.000 0.035 0.142 0.084 0.162 0.312AE-PEEDA 0.108 0.080 0.000 0.033 0.069 0.000 0.000 0.035 0.042 0.048iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.043 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.146BPEA 0.107 0.106 0.059 0.022 0.081 0.000 0.175 0.080 0.210 0.374Others 2.935 3.026 0.992 0.725 0.939 0.685 3.151 0.949 2.575 3.282MEA Conversion, % 33.53 37.20 19.34 18.02 20.14 15.44 33.80 22.92 37.97 59.15DETA Conversion, % 13.21 13.72 7.91 8.64 9.40 6.34 16.63 10.76 19.16 28.71Acyclic(N4), % 93.03 93.76 95.63 96.18 96.79 97.22 97.03 96.87 96.92 95.83Acyclic(N5), % 81.55 87.74 90.59 90.79 90.93 96.73 89.33 91.76 91.91 91.11.SIGMA.(N5)/.SIGMA.(N4), 0.42 0.38 0.34 0.29 0.29 0.24 0.31 0.35 0.48 0.67weight ratioAcyclic(N4)/cyclic 3.65 4.07 6.72 6.26 6.87 7.52 5.87 6.61 5.71 5.24(< = N4), weight ratio__________________________________________________________________________
TABLE XXIV__________________________________________________________________________ Example No. 234 235 236 237 238 239 240 241 242 243__________________________________________________________________________Catalyst Type X X X X X X X X X XCatalyst weight, gm 83.01 83.01 83.01 83.01 83.01 83.01 83.01 83.01 83.01 83.01Pressure, psig 603 596 599 599 601 597 603 603 602 603Temperature, .degree.C. 271 278 260 271 260 280 270 280 270 270Time on organics, hrs. 99 104 123 128 147 152 171 176 195 206.75MEA SV, gmol/hr/kgcat 3.13 3.33 3.26 3.20 3.18 3.07 2.34 2.47 2.21 2.35DETA/MEA mole ratio 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 5.97Crude product composition, wt %EDA 1.984 2.995 1.212 1.766 1.149 2.885 1.710 2.748 1.423 1.500MEA 6.383 3.073 13.003 5.647 11.598 3.611 10.193 5.664 10.816 11.721PIP 1.434 1.763 1.183 1.449 1.142 1.861 1.330 1.727 1.168 1.186DETA 32.000 30.373 38.190 32.197 37.489 30.866 31.155 29.136 31.286 32.092AEEA 0.501 0.186 1.296 0.439 1.265 0.220 0.847 0.403 0.987 1.078AEP 1.636 2.525 1.050 1.785 1.133 2.307 1.524 2.483 1.278 1.244HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.376 1.934 2.312 2.434 2.613 2.044 2.151 1.797 2.071 2.1401-TETA 12.940 12.003 11.840 13.576 13.452 12.217 10.663 10.795 10.563 10.796DAEP 0.920 1.655 0.439 1.079 0.545 1.534 0.822 1.573 0.617 0.608PEEDA 0.665 1.233 0.355 0.842 0.415 1.110 0.628 1.133 0.479 0.498DPE 0.287 0.120 0.230 0.316 0.181 0.104 0.063 0.089 0.229 0.044AE-TAEA 4.489 3.831 3.705 4.743 4.293 4.176 3.815 3.271 3.526 3.5751-TEPA 9.472 9.488 7.999 10.201 8.828 9.980 8.349 8.770 7.873 7.613AE-DAEP 0.811 1.698 0.463 0.927 0.392 1.458 0.759 1.596 0.624 0.664AE-PEEDA 0.148 0.223 0.123 0.165 0.067 0.216 0.150 0.128 0.081 0.078iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.151 0.482 0.201 0.162 0.057 0.283 0.193 0.229 0.390 0.325BPEA 0.149 0.853 0.178 0.215 0.057 0.232 0.082 0.655 0.601 0.569Others 9.595 14.536 7.200 10.480 6.385 12.915 9.485 10.732 7.587 7.371MEA Conversion, % 81.81 91.66 64.27 84.42 68.27 90.05 69.91 83.37 67.11 64.89DETA Conversion, % 45.79 51.02 37.63 47.22 39.06 49.48 45.34 49.17 43.45 42.86Acyclic(N4), % 89.11 82.25 93.25 87.74 93.37 83.84 89.43 81.83 90.51 91.84Acyclic(N5), % 91.73 80.36 92.38 91.05 95.82 86.60 91.13 82.19 87.05 87.25.SIGMA.(N5)/.SIGMA.(N4), 0.89 0.98 0.83 0.90 0.80 0.96 0.93 0.95 0.94 0.91weight ratioAcyclic(N4)/cyclic 3.10 1.91 4.34 2.93 4.70 2.06 2.93 1.80 3.35 3.61(< = N4), weight ratio__________________________________________________________________________
TABLE XXV__________________________________________________________________________ Example No. 244 245 246 247 248 249 250 251 252 253 254__________________________________________________________________________Catalyst Type Y Y Y Y Y Y Y Y Y Y YCatalyst weight, gm 84.9 84.9 84.9 84.9 82.11 84.9 84.9 84.9 84.9 84.9 84.9Pressure, psig 604 604 604 604 602 604 602 603 600 600 600Temperature, .degree.C. 268 279 258 270 259 278 269 278 279 270 270Time on organics, hrs. 24.5 27.75 47 52 71 76 95 99 118.5 139.8 141.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2 1 1MEA SV, gmol/hr/kgcat 2.66 2.74 2.85 3.15 3.30 3.27 3.01 3.14 2.91 2.26 3.32DETA/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 0.261 0.356 0.244 0.282 0.226 0.267 0.193 0.300 0.276 0.137 0.175MEA 32.096 31.884 33.649 33.262 34.748 33.604 35.331 34.218 33.615 33.551 33.298PIP 0.012 0.017 0.009 0.013 0.000 0.013 0.000 0.014 0.015 0.021 0.015DETA 53.034 52.823 55.550 57.167 58.160 57.340 58.631 55.561 55.690 57.452 57.445AEEA 0.039 0.072 0.023 0.200 0.054 0.089 0.039 0.073 0.075 0.063 0.067AEP 0.256 0.295 0.218 0.287 0.233 0.349 0.288 0.358 0.393 0.340 0.313HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 0.091 0.098 0.112 0.187 0.094 0.150 0.077 0.475 0.111 0.137 0.1711-TETA 0.144 0.122 0.087 0.577 0.076 0.434 0.092 0.000 0.343 0.416 0.498DAEP 0.024 0.031 0.016 0.056 0.000 0.021 0.000 0.067 0.044 0.030 0.027PEEDA 0.194 0.074 0.183 0.037 0.211 0.152 0.077 0.082 0.052 0.036 0.034DPE 0.069 0.085 0.053 0.027 0.094 0.065 0.061 0.044 0.047 0.082 0.055AE-TAEA 0.000 0.037 0.000 0.045 0.000 0.085 0.052 0.000 0.000 0.000 0.0001-TEPA 0.147 0.062 0.000 0.047 0.000 0.068 0.000 0.036 0.061 0.000 0.071AE-DAEP 0.000 0.000 0.000 0.000 0.024 0.060 0.027 0.091 0.114 0.028 0.000AE-PEEDA 0.000 0.168 0.000 0.000 0.000 0.000 0.000 0.041 0.000 0.129 0.332iAe-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 0.039 0.000 0.053 0.035 0.162 0.044 0.031 0.092 0.099 0.097BPEA 0.344 0.000 0.000 0.000 0.000 0.038 0.000 0.000 0.000 0.000 0.066Others 1.659 2.389 1.815 2.931 1.866 3.482 2.698 3.109 3.712 2.859 2.756MEA Conversion, % 3.06 3.91 2.16 6.89 3.11 7.25 3.34 3.38 5.38 6.32 7.15DETA Conversion, % 4.80 5.39 4.00 4.90 3.62 5.94 4.67 6.76 6.84 4.67 4.80Acyclic(N4), % 44.95 53.51 44.02 86.49 35.80 71.03 54.99 71.17 76.09 78.86 85.22Acyclic(N5), % 30.60 32.37 0.00 63.66 0.00 37.00 42.32 18.14 22.79 0.00 12.61.SIGMA.(N5)/.SIGMA.(N4), 0.92 0.75 0.00 0.16 0.13 0.50 0.40 0.30 0.45 0.36 0.72weight ratioAcyclic(N4)/cyclic 0.42 0.44 0.41 1.82 0.32 0.97 0.40 0.84 0.82 1.09 1.51(< = N4), weight ratio__________________________________________________________________________
TABLE XXVI__________________________________________________________________________ Example No. 255 256 257 258 259 260 261 262 263__________________________________________________________________________Catalyst Type Z Z Z Z Z Z Z Z ZCatalyst weight, gm 45.68 45.68 45.68 45.68 45.68 45.68 45.68 45.68 45.68Presure, psig 600 599 607 596 600 600 600 600 604Temperature, .degree.C. 269 279 260 270 270 259.6 279 270 280Time on organics, hrs. 21 28 49 54 73.5 97.5 116 121 139Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 5.74 5.87 5.23 6.08 3.67 3.99 2.29 4.68 5.77DETA/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 4.265 6.176 3.433 3.075 3.788 3.313 4.920 3.283 4.944MEA 5.796 3.354 10.079 7.161 8.233 12.638 5.859 8.995 7.083PIP 2.117 2.992 1.443 1.595 1.901 1.711 3.037 1.662 2.421DETA 28.085 21.574 33.585 28.671 28.468 35.387 22.837 31.649 26.907AEEA 0.099 0.063 0.399 0.132 0.103 0.381 0.025 0.197 0.067AEP 4.039 6.092 2.608 3.219 3.601 3.484 6.074 3.491 5.328HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 3.229 1.766 3.587 3.434 2.819 2.812 1.936 3.537 2.2411-TETA 11.677 6.932 11.244 11.553 10.261 9.480 6.501 11.947 9.241DAEP 2.387 3.807 1.767 1.907 1.991 1.653 4.685 2.133 3.545PEEDA 1.116 1.889 0.855 0.890 0.958 0.844 2.020 0.989 1.785DPE 0.174 0.405 0.101 0.132 0.139 0.113 0.580 0.315 0.262AE-TAEA 5.681 3.174 5.080 5.634 4.681 3.953 2.940 5.597 3.6771-TEPA 8.664 6.535 6.720 7.856 6.920 5.613 3.566 7.833 6.809AE-DAEP 0.935 0.738 0.803 0.708 0.722 0.579 0.757 0.823 1.937AE-PEEDA 0.258 1.129 0.214 0.198 0.223 0.219 0.904 0.272 0.737iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.055 0.256 0.050 0.037 0.048 0.047 0.237 0.050 0.057BPEA 0.975 0.822 0.665 0.847 0.688 0.813 0.350 0.801 0.858Others 8.808 15.412 6.548 7.053 6.595 5.262 19.371 7.036 12.602MEA Conversion, % 84.08 90.34 72.07 79.20 75.41 64.40 83.73 75.68 81.06DETA Conversion, % 54.16 63.06 44.68 50.52 49.47 40.75 62.31 49.14 57.23Acyclic(N4), % 80.21 58.78 84.49 83.65 80.90 82.49 53.67 81.83 67.25Acyclic(N5), % 86.58 76.69 87.20 88.29 87.35 85.23 74.32 87.34 74.50.SIGMA.(N5)/.SIGMA.(N4), 0.89 0.86 0.77 0.85 0.82 0.75 0.56 0.81 0.82weight ratioAcyclic(N4)/cyclic 1.52 0.57 2.19 1.94 1.52 1.58 0.51 1.80 0.86(< = N4), weight ratio__________________________________________________________________________
TABLE XXVII__________________________________________________________________________ Example No. 264 265 266 267 268 269 270 271 272__________________________________________________________________________Catalyst Type AA AA AA AA AA AA AA AA AACatalyst weight, gm 71.9 71.9 71.9 71.9 71.9 71.9 71.9 71.9 71.9Pressure, psig 604 604 609 606 600 600 603 602 602Temperature, .degree.C. 270 282 258 272 260 280 273 281 272Time on organics, hrs. 20.5 25.5 44.5 49.5 69.3 93.3 116.5 121.5 138.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.36 3.46 3.43 3.50 3.55 3.41 3.50 3.67 3.49DETA/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 0.654 1.188 0.880 0.700 0.372 1.659 0.860 1.397 0.841MEA 26.367 22.170 24.384 27.194 29.909 21.016 27.518 23.168 26.560PIP 0.812 1.365 0.882 0.772 0.000 1.711 0.812 1.473 0.833DETA 51.269 45.690 48.835 51.840 55.476 43.224 51.818 46.089 52.002AEEA 2.016 1.702 1.570 1.900 1.779 1.481 1.827 1.619 1.976AEP 0.692 1.168 0.882 0.598 0.374 1.439 0.624 1.193 0.678HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.323 1.418 1.256 1.217 0.943 1.295 1.188 1.308 1.2161-TETA 7.359 8.836 7.770 6.793 5.048 8.777 6.824 8.418 7.095DEAP 0.163 0.347 0.300 0.112 0.071 0.485 0.130 0.370 0.143PEEDA 0.160 0.417 0.373 0.120 0.076 0.528 0.145 0.432 0.153DPE 0.046 0.069 0.061 0.042 0.025 0.114 0.046 0.034 0.050AE-TAEA 1.015 1.431 1.257 0.863 0.494 1.551 0.865 1.450 0.9231-TEPA 2.990 4.899 4.463 2.563 1.436 5.428 2.725 4.968 2.853AE-DAEP 0.242 0.305 0.326 0.045 0.074 0.345 0.060 0.264 0.065AE-PEEDA 0.106 0.077 0.079 0.000 0.000 0.094 0.062 0.187 0.038iAE-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 0.031 0.052 0.046 0.123 0.080 0.273 0.127 0.070 0.049Others 1.656 3.848 3.595 1.579 0.943 4.584 1.700 3.838 1.946MEA Conversion, % 29.19 40.08 35.05 26.39 18.82 42.93 26.19 38.13 28.97DETA Conversion, % 18.17 26.61 22.69 16.60 10.51 30.24 17.39 26.86 17.35Acyclic(N4), % 95.92 92.50 92.49 96.69 97.20 89.50 96.15 92.08 96.01Acyclic(N5), % 91.34 93.59 92.70 95.32 92.60 90.73 93.52 92.49 96.12.SIGMA.(N5)/.SIGMA.(N4), 0.48 0.61 0.63 0.43 0.34 0.68 0.46 0.66 0.45weight ratioAcyclic(N4)/cyclic 4.64 3.05 3.61 4.87 10.96 2.33 4.56 2.78 4.48(< = N4), weight ratio__________________________________________________________________________
TABLE XXVIII__________________________________________________________________________ Example No. 273 274 275 276 277 278 279 280 281__________________________________________________________________________Catalyst Type BB BB BB BB BB BB BB BB BBCatalyst weight, gm 47.15 47.15 47.15 47.15 47.15 47.15 47.15 47.15 47.15Presure, psig 603 604 597 593 600 609 600 601 601Temperature, .degree.C. 270 281 258 272 280 273 281 272 272Time on organics, hrs. 20.5 25.5 44.5 49.5 93.3 116.5 121.5 138.5 143.25Duration of run, hrs. 2 2 2 2 1 2 2 2 2MEA SV, gmol/hr/kgcat 5.62 5.50 6.38 5.77 5.23 4.89 6.12 5.90 6.45DETA/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 4.112 6.049 3.022 3.411 5.550 3.212 4.820 3.441 2.793MEA 3.993 1.805 8.392 5.992 2.263 7.178 3.892 6.533 8.131PIP 2.090 2.764 1.493 1.835 2.928 1.697 2.331 1.856 1.521DETA 26.200 19.797 30.716 29.072 19.595 30.928 25.883 27.399 32.697AEEA 0.105 0.029 0.466 0.193 0.059 0.257 0.082 0.253 0.337AEP 3.816 5.459 2.748 3.098 5.455 2.783 4.440 3.792 2.683HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 3.246 1.816 3.371 3.690 1.636 3.637 1.211 3.154 3.6571-TETA 12.248 7.991 11.446 12.890 7.985 12.535 9.944 11.428 12.152DAEP 2.327 3.836 1.908 1.821 3.625 1.607 2.852 2.506 1.457PEEDA 1.147 2.001 1.029 0.933 1.998 0.854 1.534 1.473 0.870DPE 0.205 0.259 0.072 0.159 0.343 0.212 0.287 0.292 0.199AE-TAEA 5.841 3.653 5.224 6.189 3.051 6.144 4.652 4.999 5.5661-TEPA 9.617 6.279 8.218 9.146 4.846 8.976 8.411 7.886 8.254AE-DAEP 1.138 2.226 1.270 0.744 0.976 0.196 0.637 0.703 0.282AE-PEEDA 0.133 0.798 0.566 0.032 1.236 0.237 0.789 0.817 0.091iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.198 0.335 0.262 0.062 0.124 0.064 0.176 0.106 0.138BPEA 0.494 1.127 0.826 0.441 0.203 1.316 1.347 1.252 1.167Others 13.100 17.605 11.271 10.063 19.810 9.418 16.332 12.551 9.604MEA Conversion, % 89.29 94.88 77.77 83.74 93.38 80.79 89.55 82.50 78.25DETA Conversion, % 58.24 66.61 51.64 53.13 65.93 50.81 58.69 56.38 48.01Acyclic(N4), % 80.81 61.67 83.12 85.06 61.73 85.82 70.48 77.35 86.22Acyclic(N5), % 88.73 68.89 82.14 92.30 75.68 89.29 81.59 81.74 89.16.SIGMA. (N5)/.SIGMA.(N4), 0.91 0.91 0.92 0.85 0.67 0.90 1.01 0.84 0.85weight ratioAcyclic(N4)/cyclic 1.62 0.68 2.04 2.11 0.67 2.26 0.97 1.47 2.35(< = N4), weight ratio__________________________________________________________________________ Example No. 282 283 284 285 286 287 288 289 290__________________________________________________________________________Catalyst Type BB BB BB BB BB BB BB BB BBCatalyst weight, gm 47.15 47.15 47.15 47.15 47.15 47.15 47.15 47.15 47.15Pressure, psig 603 602 601 602 596 599 600 600 600Temperature, .degree.C. 270 280 260 269 259 269 269 279.6 268Time on organics, hrs. 22.5 27.5 46.5 51.5 70.5 99.5 120 143 169.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.97 4.30 3.85 2.94 0.75 5.31 5.03 4.80 3.32DETA/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 2.967 4.366 4.440 2.967 4.460 1.952 3.142 4.055 2.453MEA 9.344 4.942 4.115 7.299 4.769 11.879 10.054 6.454 12.691PIP 1.511 2.037 2.043 1.452 2.132 1.272 1.700 2.182 1.366DETA 31.637 26.975 25.016 30.734 25.564 38.106 32.444 26.800 38.319AEEA 0.424 0.162 0.130 0.465 0.229 0.767 0.506 0.183 0.649AEP 2.464 3.612 3.730 2.436 3.835 1.957 3.105 4.023 2.028HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 3.232 3.170 3.039 4.030 3.514 3.588 2.814 2.467 3.5441-TETA 11.069 12.118 12.039 13.420 13.075 11.521 10.058 9.825 12.044DAEP 1.231 2.138 2.332 1.243 2.045 0.861 1.515 2.269 0.889PEEDA 0.679 1.195 1.326 0.704 1.131 0.508 0.922 1.458 0.524DPE 0.187 0.300 0.338 0.255 0.476 0.141 0.254 0.309 0.124AE-TAEA 5.103 5.422 5.331 6.126 5.933 4.797 4.017 4.146 4.6101-TEPA 7.681 9.105 9.262 8.935 9.548 6.845 6.630 7.426 6.884AE-DAEP 0.028 0.438 0.477 0.260 0.377 0.367 0.846 1.348 0.370AE-PEEDA 0.645 0.119 0.143 0.119 0.141 0.096 0.119 0.616 0.106iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.437 0.190 0.276 0.126 0.050 0.048 0.028 0.092 0.029BPEA 0.997 0.316 0.321 0.381 0.328 0.593 0.605 0.273 0.533Others 6.554 13.105 14.254 9.326 11.795 5.441 9.162 13.636 4.287MEA Conversion, % 73.30 86.63 88.77 80.18 87.07 67.40 71.78 82.09 65.35DETA Conversion, % 46.27 56.62 59.43 50.41 58.82 37.84 45.87 55.81 37.82Acyclic(N4), % 87.21 80.80 79.05 88.79 81.96 90.91 82.71 75.29 91.03Acyclic(N5), % 85.85 93.18 92.31 94.44 94.53 91.34 86.95 83.25 91.71.SIGMA.(N5)/.SIGMA.(N4), 0.91 0.82 0.83 0.81 0.81 0.77 0.79 0.85 0.73weight ratioAcyclic(N4)/cyclic 2.36 1.65 1.54 2.87 1.72 3.19 1.72 1.20 3.16(< = N4), weight ratio__________________________________________________________________________
TABLE XXIX__________________________________________________________________________ Example No. 291 292 293 294 295 296 297 298 299 300__________________________________________________________________________Catalyst Type CC CC CC CC CC CC CC CC CC CCCatalyst weight, gm 76.68 76.68 76.68 76.68 76.68 76.68 76.68 76.68 76.68 76.68Pressure, psig 603 603 604 604 604 604 602 600 600 603Temperature, .degree.C. 270 260 269 259 280 280 269 269 279.6 268Time on organics, hrs. 22.5 46.5 51.5 70.5 75.5 94.5 99.5 120 143 169.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.56 3.18 3.05 2.39 2.57 2.86 3.10 2.58 2.14 2.10DETA/MEA mole ratio 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 5.97Crude product composition, wt. %EDA 1.048 1.891 1.635 0.886 2.023 1.862 0.964 1.307 2.134 1.598MEA 15.586 7.180 13.602 16.846 6.993 5.180 14.419 11.949 4.391 10.047PIP 0.813 1.493 1.323 0.749 1.617 1.560 1.056 1.181 1.690 1.287DETA 41.901 34.342 39.594 43.641 34.966 31.278 43.144 40.674 33.084 40.233AEEA 1.865 0.611 1.010 2.381 0.717 0.512 2.061 1.865 0.489 1.972AEP 0.823 1.517 1.156 0.704 1.562 1.651 0.963 1.108 1.845 1.344HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.659 2.739 2.487 2.206 2.576 2.486 2.470 2.584 2.664 2.7781-TETA 11.989 13.676 12.245 10.267 13.010 12.812 11.950 12.589 14.102 14.021DAEP 0.232 0.654 0.419 0.182 0.622 0.734 0.275 0.343 0.814 0.472PEEDA 0.217 0.518 0.333 0.166 0.508 0.588 0.265 0.328 0.634 0.384DPE 0.109 0.083 0.058 0.039 0.100 0.095 0.052 0.061 0.132 0.148AE-TAEA 3.022 4.382 3.620 1.989 4.314 4.182 3.097 3.397 4.800 3.5281-TEPA 5.378 8.807 6.947 3.856 8.743 8.887 6.071 6.875 10.097 7.285AE-DAEP 0.000 0.169 0.298 0.077 0.555 0.161 0.332 0.223 0.191 0.386AE-PEEDA 0.213 0.106 0.056 0.030 0.119 0.104 0.049 0.039 0.121 0.060iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.429 0.057 0.000 0.000 0.079 0.078 0.045 0.000 0.109 0.086BPEA 0.423 0.255 0.529 0.212 0.715 0.986 0.407 0.447 1.153 0.657Others 2.432 7.971 4.837 2.430 8.651 8.353 4.000 4.471 9.150 4.134MEA Conversion, % 55.76 79.54 62.13 50.35 80.43 84.46 60.32 66.53 87.79 72.35DETA Conversion, % 29.31 41.82 34.48 23.55 41.85 44.25 29.45 32.30 45.34 34.20Acyclic(N4), % 96.35 92.90 94.78 96.99 92.69 91.52 96.06 95.40 91.39 94.36Acyclic(N5), % 88.75 95.74 92.28 94.82 89.89 90.77 91.66 93.55 90.44 90.10.SIGMA.(N5)/.SIGMA.(N4), 0.62 0.78 0.74 0.48 0.86 0.86 0.67 0.69 0.90 0.67weight ratioAcyclic(N4)/cyclic 6.67 3.85 4.48 6.78 3.54 3.31 5.53 5.02 3.28 4.62(< = N4), weight ratio__________________________________________________________________________
TABLE XXX__________________________________________________________________________ Example No. 301 302 303 304 305 306 307 308 309 310__________________________________________________________________________Catalyst Type DD DD DD DD DD DD DD DD DD DDCatalyst weight, gm 78.75 78.75 78.75 78.75 78.75 78.75 78.75 78.75 78.75 78.75Pressure, psig 598 598 599 598 600 600 598 600 598 600Temperature, .degree.C. 269 279 260 270 270 259.6 279 270 280 270Time on organics, hrs. 21 28 49 54 73.5 97.5 116 121 139 144Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 2.92 2.87 3.06 2.85 2.60 2.98 2.80 2.99 2.81 2.96DETA/MEA mole ratio 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 5.97Crude product composition, wt. %EDA 1.555 1.668 1.004 0.978 0.998 0.533 2.192 1.116 1.691 0.974MEA 15.132 10.654 18.325 16.432 15.110 22.024 8.483 16.234 7.965 14.943PIP 0.978 1.343 0.749 0.856 0.926 0.581 1.662 1.112 1.577 1.057DETA 41.054 38.593 44.607 43.072 41.241 51.032 35.320 45.272 36.976 44.374AEEA 1.683 0.873 1.751 1.997 1.834 2.629 0.512 1.883 0.650 1.955AEP 1.101 1.347 0.771 0.821 0.835 0.570 1.905 0.982 1.561 1.000HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.712 2.489 2.232 2.241 2.226 1.861 2.166 2.390 2.589 2.5111-TETA 11.777 11.906 10.383 10.387 10.429 8.845 11.724 11.589 13.232 12.136DAEP 0.423 0.486 0.280 0.215 0.235 0.126 0.995 0.266 0.649 0.285PEEDA 0.327 0.415 0.253 0.183 0.199 0.101 0.736 0.226 0.512 0.249DPE 0.088 0.183 0.098 0.092 0.091 0.057 0.262 0.089 0.219 0.098AE-TAEA 3.411 3.691 2.918 2.501 2.621 1.429 3.662 3.017 4.503 3.1211-TEPA 6.041 6.960 5.789 4.661 4.999 2.823 8.129 5.730 9.114 6.079AE-DAEP 0.397 0.339 0.351 0.199 0.231 0.053 1.154 0.242 0.570 0.278AE-PEEDA 0.058 0.077 0.059 0.052 0.032 0.000 0.223 0.032 0.163 0.042iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.052 0.153 0.049 0.072 0.067 0.000 0.208 0.077 0.070 0.097BPEA 0.695 0.772 0.603 0.425 0.457 0.177 0.094 0.547 0.803 0.556Others 4.145 4.991 3.687 2.354 2.636 1.310 9.047 2.757 7.406 3.016MEA Conversion, % 58.37 69.49 50.38 52.25 55.02 39.54 76.37 56.07 78.27 59.37DETA Conversion, % 32.88 34.31 28.22 25.62 27.04 16.74 41.52 27.19 40.06 28.29Acyclic(N4), % 94.53 92.99 95.23 96.26 96.01 97.42 87.46 96.01 91.98 95.86Acyclic(N5), % 88.72 88.82 89.13 90.54 90.63 94.86 87.54 90.69 89.45 90.43.SIGMA.(N5)/.SIGMA.(N4), 0.70 0.77 0.74 0.60 0.64 0.41 0.85 0.66 0.88 0.67weight ratioAcyclic(N4)/cyclic 4.97 3.81 5.86 5.83 5.53 7.46 2.50 5.23 3.50 5.45(< = N4), weight ratio__________________________________________________________________________
TABLE XXXI__________________________________________________________________________ Example No. 311 312 313 314 315 316 317 318 319 320__________________________________________________________________________Catalyst Type EE EE EE EE EE EE EE EE EE EECatalyst weight, gm 76.67 76.67 76.67 76.67 76.67 76.67 76.67 76.67 76.67 76.67Pressure, psig 599 599 609 599 600 598 596 598 600 599Temperature, .degree.C. 270 280 260 269 259 280 280 269 269 268Time on organics, hrs. 22.5 27.5 46.5 51.5 70.5 75.5 94.5 99.5 120 169.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.05 3.06 2.79 3.10 3.07 3.13 3.03 3.01 3.05 3.15DETA/MEA mole ratio 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 5.97Crude product composition, wt. %EDA 1.520 2.437 2.447 1.228 1.029 2.414 2.547 1.320 1.437 1.242MEA 14.652 8.505 6.424 13.718 18.262 7.632 6.416 14.174 12.516 13.988PIP 1.110 1.615 1.625 1.089 0.811 1.685 1.788 1.154 1.228 1.100DETA 39.856 33.953 30.620 42.604 44.433 34.076 32.533 40.980 39.040 42.773AEEA 1.060 0.447 0.314 1.855 1.945 0.437 0.334 1.170 1.071 1.048AEP 1.075 1.737 1.834 1.025 0.733 1.846 2.086 1.119 1.173 1.187HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.436 2.526 2.311 2.830 2.495 2.424 2.285 2.594 2.614 2.5921-TETA 11.953 13.615 12.962 13.423 11.709 13.253 12.977 12.761 12.998 14.044DAEP 0.316 0.845 0.960 0.297 0.197 0.863 1.049 0.408 0.461 0.325PEEDA 0.271 0.647 0.738 0.284 0.177 0.663 0.796 0.337 0.392 0.267DPE 0.114 0.099 0.099 0.049 0.040 0.099 0.102 0.071 0.074 0.052AE-TAEA 3.524 4.505 4.333 3.359 2.704 4.359 4.387 3.710 3.897 3.4011-TEPA 6.384 9.138 9.198 6.628 5.017 9.080 9.494 6.780 7.415 6.586AE-DAEP 0.000 0.248 0.279 0.314 0.207 0.679 0.267 0.307 0.269 0.300AE-PEEDA 0.229 0.135 0.140 0.042 0.063 0.126 0.123 0.032 0.057 0.054iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.553 0.191 0.210 0.000 0.000 0.052 0.093 0.000 0.033 0.000BPEA 0.522 0.338 0.365 0.442 0.300 0.794 0.831 0.530 0.577 0.532Others 3.075 9.229 10.383 4.003 2.618 9.258 10.540 4.653 5.267 2.788MEA Conversion, % 58.39 76.75 81.53 63.00 49.80 79.10 82.29 61.34 65.43 62.89DETA Conversion, % 32.73 44.85 47.68 31.70 27.42 44.55 46.62 33.56 35.92 30.74Acyclic(N4), % 95.36 91.03 89.48 96.26 97.17 90.61 88.68 94.65 94.40 96.27Acyclic(N5), % 88.37 93.73 93.16 92.61 93.12 89.06 91.35 92.35 92.35 91.85.SIGMA.(N5)/.SIGMA.(N4), 0.74 0.82 0.85 0.64 0.57 0.87 0.88 0.70 0.74 0.63weight ratioAcyclic(N4)/cyclic 4.99 3.27 2.91 5.92 7.25 3.04 2.62 4.97 4.69 5.68(< = N4), weight ratio__________________________________________________________________________
TABLE XXXII__________________________________________________________________________ Example No. 321 322 323 324 325 326 327 328 329__________________________________________________________________________Catalyst Type FF FF FF FF FF FF FF FF FFCatalyst weight, gm 81.02 81.02 81.02 81.02 81.02 81.02 81.02 81.02 81.02Pressure, psig 598 598 598 598 598 598 600 600 600Temperature, .degree.C. 258 270 259 278 269 278 279 270 270Time on organics, hrs. 47 52 71 76 95 99 118.5 139.8 141.5Duration of run, hrs. 2 2 2 2 2 2 2 1 1MEA SV, gmol/hr/kgcat 2.59 2.69 2.76 2.69 2.62 2.89 2.50 2.61 2.85DETA/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 1.431 1.466 0.836 2.026 1.389 1.898 3.937 1.319 1.270MEA 20.803 15.928 21.573 8.455 13.153 5.684 3.430 11.218 12.033PIP 0.619 0.793 0.421 1.275 0.987 1.265 2.108 1.046 0.995DETA 41.470 40.511 47.612 36.072 40.931 31.699 26.932 37.630 37.696AEEA 1.655 2.044 2.654 0.991 1.869 0.695 0.297 1.784 1.787AEP 1.227 0.888 0.525 1.430 1.026 1.530 3.019 1.099 0.994HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.792 2.202 1.893 2.343 2.432 2.392 1.670 2.598 2.3081-TETA 9.207 11.790 9.627 13.461 13.115 13.772 11.582 14.083 12.425DAEP 0.616 0.258 0.103 0.671 0.399 0.778 1.863 0.456 0.383PEEDA 0.451 0.211 0.071 0.519 0.296 0.575 1.351 0.364 0.034DPE 0.029 0.076 0.066 0.203 0.107 0.217 0.107 0.049 0.059AE-TAEA 2.172 3.076 1.560 4.364 3.434 4.598 0.163 3.800 3.5881-TEPA 4.520 5.662 2.989 9.213 7.036 9.871 9.389 7.945 7.481AE-DAEP 0.421 0.185 0.102 0.530 0.226 6.503 0.543 0.066 0.134AE-PEEDA 0.029 0.036 0.030 0.116 0.035 0.100 0.907 0.030 0.098iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.023 0.000 0.000 0.223 0.050 0.264 0.161 0.068 0.138BPEA 0.388 0.045 0.026 0.807 0.056 1.316 1.078 0.184 0.220Others 3.269 3.950 1.862 7.511 4.907 4.583 16.344 5.932 7.028MEA Conversion, % 40.86 54.65 39.37 76.88 63.86 84.34 90.23 68.77 66.03DETA Conversion, % 29.93 31.45 20.47 41.38 33.16 48.10 54.39 37.75 36.75Acyclic(N4), % 90.94 96.25 97.95 91.90 95.09 91.15 79.97 95.05 96.87Acyclic(N5), % 88.61 97.05 96.63 89.01 96.62 63.88 78.03 97.13 94.95.SIGMA.(N5)/.SIGMA.(N4), 0.62 0.62 0.40 0.89 0.66 1.28 0.74 0.69 0.77weight ratioAcyclic(N4)/cyclic 3.74 6.29 9.71 3.86 5.52 3.70 1.57 5.53 5.98(< = N4), weight ratio__________________________________________________________________________
TABLE XXXIII__________________________________________________________________________ Example No. 330 331 332 333 334 335 336 337 338__________________________________________________________________________Catalyst Type GG GG GG GG GG GG GG GG GGCatalyst weight, gm 68 68 68 68 68 68 68 68 68Pressure, psig 606 599 602 606 593 593 601 600 600Temperature, .degree.C. 270 270 280 260 270 260 280 280 270Time on organics, hrs. 7 26 30.5 50 55 74 79 98.8 123Duration of run, hrs. 2 2 1 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.97 3.90 3.93 3.98 3.96 3.94 3.97 3.93 3.85DETA/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 0.750 0.869 1.269 0.502 0.696 1.589 1.188 1.273 0.810MEA 14.139 13.058 7.841 19.884 13.962 19.078 8.661 6.995 13.582PIP 0.946 1.041 1.264 0.614 0.883 0.667 1.206 1.218 0.953DETA 42.338 40.333 34.679 47.727 41.491 46.874 37.218 33.635 40.430AEEA 1.641 1.480 0.679 2.213 1.609 2.241 0.609 0.617 1.541AEP 0.987 1.041 1.527 0.599 0.913 0.603 1.467 1.500 0.961HEP 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 2.5551-TETA 12.825 13.469 13.932 10.488 12.891 10.468 13.856 13.911 12.446DAEP 0.340 0.387 0.763 0.170 0.305 0.165 0.693 0.770 0.335PEEDA 0.302 0.336 0.601 0.150 0.277 0.146 0.549 0.605 0.284DPE 0.132 0.150 0.301 0.094 0.099 0.099 0.088 0.118 0.077AE-TAEA 3.574 3.998 4.830 2.253 3.538 2.309 4.432 4.606 3.5001-TEPA 7.216 7.943 9.991 4.612 7.184 4.724 9.147 9.831 7.304AE-DAEP 0.088 0.082 0.204 0.154 0.134 0.064 0.601 0.879 0.328AE-PEEDA 0.155 0.158 0.380 0.028 0.223 0.074 0.067 0.125 0.039iAE-PEEDA 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 0.048BPEA 0.508 0.179 1.040 0.229 0.611 0.231 0.804 0.839 0.472Others 5.025 5.875 9.178 2.946 5.812 3.348 7.734 8.939 4.826MEA conversion, % 62.09 64.96 79.02 46.40 62.51 48.13 76.57 80.72 62.33DETA conversion, % 32.54 35.67 44.85 23.54 33.79 24.26 40.15 44.90 33.36Acyclic(N4), wt. % 95.24 94.91 90.90 96.85 95.77 96.87 92.56 91.71 95.57Acyclic(N5), wt. % 93.19 96.09 87.98 93.64 89.81 94.07 89.76 87.00 92.42.SIGMA.(N5)/.SIGMA.(N4), 0.71 0.73 0.92 0.56 0.74 0.57 0.85 0.92 0.74weight ratioAcyclic(N4)/cyclic 5.72 5.50 3.73 7.82 6.22 7.57 4.14 3.93 5.75(< = N4), weight ratio__________________________________________________________________________ Example No. 339 340 341 342 343 344 345 346 347 348__________________________________________________________________________Catalyst Type GG GG GG GG GG GG GG GG GG GGCatalyst weight, gm 68 68 68 68 68 68 68 68 68 68Pressure, psig 596 598 602 603 602 602 603 603 603 603Temperature, .degree.C. 271 282 260 270 260 281 272 280 272 271Time on organics, hrs. 158 163 182 187 206 211 272 235 254 257.5Duration of run, hrs. 2 2 2 2 83.7 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.92 3.89 3.99 3.83 0.09 3.85 3.80 3.88 3.86 4.03DETA/MEA mole ratio 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 5.97Crude product composition, wt. %EDA 1.086 1.518 0.564 0.960 0.630 1.769 1.921 2.220 1.641 1.650MEA 13.203 6.960 18.056 12.558 17.829 6.838 12.002 5.827 11.663 13.072PIP 1.186 1.446 0.765 1.101 0.770 1.362 1.263 1.380 1.178 1.205DETA 40.181 35.494 45.781 40.874 44.267 34.368 39.115 30.652 38.907 40.441AEEA 1.261 0.505 2.117 1.385 2.108 0.517 1.158 0.441 1.197 1.308AEP 1.136 1.798 0.738 1.161 0.699 1.725 1.205 1.595 1.179 1.119HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.661 2.671 2.384 2.732 2.320 2.531 2.548 2.402 2.575 2.5131-TETA 13.232 14.206 11.386 13.549 11.117 13.437 12.752 13.162 12.893 12.524DAEP 0.452 0.939 0.225 0.438 0.196 0.889 0.485 0.981 0.469 0.410PEEDA 0.372 0.692 0.187 0.361 0.175 0.670 0.383 0.728 0.375 0.335DPE 0.076 0.107 0.056 0.091 0.033 0.111 0.077 0.133 0.082 0.076AE-TAEA 4.013 4.667 2.669 3.990 2.705 4.603 4.023 4.890 3.878 3.7701-TEPA 8.152 9.680 5.588 8.225 5.696 9.840 8.145 10.433 8.054 7.706AE-DAEP 0.401 0.783 0.156 0.382 0.201 0.171 0.377 0.235 0.379 0.324AE-PEEDA 0.047 0.080 0.028 0.051 0.028 0.114 0.042 0.161 0.048 0.037iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.057 0.105 0.046 0.043 0.036 0.053 0.049 0.706 0.047 0.046BPEA 0.607 0.902 0.324 0.630 0.311 0.897 0.644 1.020 0.619 0.582Others 5.537 8.116 3.310 5.711 3.339 10.005 5.502 13.484 5.564 5.184MEA conversion, % 64.77 81.20 51.33 66.74 50.94 81.35 67.32 84.30 67.93 64.52DETA conversion, % 36.28 43.03 26.65 35.67 27.60 44.30 36.70 50.93 36.43 34.77Acyclic(N4), wt. % 94.64 90.67 96.72 94.81 97.08 90.53 94.19 89.41 94.35 94.83Acyclic(N5), wt. % 91.63 88.47 93.71 91.70 93.58 92.12 91.63 87.84 91.61 92.07.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.79 0.87 0.62 0.78 0.65 0.89 0.82 1.00 0.79 0.79Acyclic(N4)/cyclic(< = N4), 4.93 3.39 6.99 5.16 7.17 3.36 4.48 3.23 4.71 4.78weight ratio__________________________________________________________________________ Example No. 349 350 351 352 353 354 355 356 357__________________________________________________________________________Catalyst Type GG GG GG GG GG GG GG GG GGCatalyst weight, gm 67.2 67.2 67.2 67.2 67.2 67.2 67.2 67.2 67.2Pressure, 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 28.5 47.5 52.5 71 76.5 96.5 99Duration of run, hrs. 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.59 4.81 4.66 4.74 4.80 4.79 4.46 4.63 4.60DETA/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 0.515 0.541 1.593 0.567 0.832 0.445 1.675 0.932 0.995MEA 23.588 25.727 18.012 26.580 21.992 27.189 13.854 20.859 20.291PIP 0.888 1.118 1.953 1.009 1.390 0.957 1.810 1.493 1.486DETA 54.811 54.100 50.845 55.433 53.042 56.685 51.796 53.039 51.623AEEA 0.344 0.802 0.233 0.360 0.208 0.377 0.150 0.478 0.210AEP 0.883 0.858 1.884 0.856 1.352 0.775 2.177 1.423 1.423HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.618 1.490 1.878 1.474 1.695 1.397 1.977 1.858 1.9551-TETA 7.964 7.269 9.198 6.586 8.327 6.490 9.962 8.880 10.270DAEP 0.114 0.093 0.645 0.301 0.154 0.207 0.692 0.412 0.178PEEDA 0.081 0.064 0.387 0.144 0.104 0.117 0.359 0.162 0.125DPE 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-TAEA 0.000 0.088 0.246 0.000 0.102 0.000 1.894 0.109 0.0001-TEPA 0.664 0.704 1.555 0.500 0.975 0.246 3.556 1.157 1.321AE-DAEP 0.000 0.223 0.372 0.000 0.000 0.000 0.114 0.133 0.326AE-PEEDA 0.000 0.000 0.099 0.000 0.175 0.000 0.075 0.000 0.069iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.168 0.000 0.059 0.000 0.423 0.000 0.000 0.083 0.512BPEA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000Others 1.532 0.963 2.990 1.492 2.047 0.994 0.880 1.861 2.579MEA conversion, % 34.18 28.60 49.97 27.10 38.81 25.75 61.46 42.13 44.20DETA conversion, % 9.11 10.77 16.06 9.64 12.29 7.99 14.37 12.55 15.64Acyclic(N4), wt. % 98.01 98.23 91.48 94.77 97.49 96.05 91.91 94.93 97.59Acyclic(N5), wt. % 79.79 78.07 77.26 100.00 64.30 100.00 96.64 85.40 59.30.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.09 0.11 0.19 0.06 0.16 0.03 0.43 0.13 0.18Acyclic(N4)/cyclic(< = N4), 4.87 4.11 2.27 3.49 3.34 3.83 2.37 3.08 3.81weight ratio__________________________________________________________________________
TABLE XXXIV__________________________________________________________________________ Example No. 358 359 360 361 362 363 364 365 366__________________________________________________________________________Catalyst Type HH HH HH HH HH HH HH HH HHCatalyst weight, gm 69.34 69.34 69.34 69.34 69.34 69.34 69.34 69.34 69.34Pressure, psig 604 603 603 604 604 603 603 600 600Temperature, .degree.C. 270 270 280 260 270 260 280 280 270Time on organics, hrs. 7 26 30.5 50 55 74 79 98.8 123Duration of run, hrs. 2 2 1 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.33 4.26 4.21 4.20 4.33 4.20 4.17 4.26 4.16DETA/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 0.805 1.034 1.662 0.510 0.908 0.544 1.363 2.077 0.963MEA 14.316 13.747 10.093 20.646 15.418 19.410 8.991 9.550 15.047PIP 0.832 0.927 1.260 0.542 0.841 0.555 1.085 1.325 0.906DETA 41.647 40.641 36.709 48.819 43.537 47.902 35.150 32.997 41.105AEEA 1.392 1.332 0.661 2.056 1.526 2.142 0.718 0.580 1.445AEP 0.990 1.057 1.455 0.554 0.915 0.588 1.336 1.810 0.927HEP 0.000 0.000 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 2.593 1.994 2.4431-TETA 13.276 13.074 12.859 9.750 12.028 10.013 12.850 10.946 11.547DAEP 0.416 0.470 0.726 0.152 0.358 0.171 0.754 1.270 0.373PEEDA 0.321 0.347 0.527 0.130 0.270 0.147 0.531 0.858 0.292DPE 0.151 0.167 0.208 0.055 0.159 0.073 0.126 0.164 0.196AE-TAEA 4.148 4.074 4.997 2.219 3.441 2.254 4.357 3.447 3.1931-TEPA 7.057 7.074 8.378 3.718 6.209 3.871 8.283 7.231 6.092AE-DAEP 0.081 0.074 0.124 0.145 0.075 0.247 1.053 1.912 0.489AE-PEEDA 0.148 0.141 0.238 0.027 0.117 0.067 0.154 0.294 0.065iAE-PEEDA 0.000 0.000 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 0.309 0.130 0.070BPEA 0.582 0.570 0.800 0.207 0.479 0.205 0.737 0.613 0.415Others 5.099 5.415 7.215 2.423 4.615 2.781 8.931 12.620 4.609MEA conversion, % 61.90 63.00 72.52 43.91 58.54 46.90 75.19 73.83 57.94DETA conversion, % 34.13 35.00 40.60 21.18 30.42 22.12 42.36 46.26 31.71Acyclic(N4), wt. % 94.82 94.20 91.41 97.28 94.93 96.93 91.63 84.95 94.20Acyclic(N5), wt. % 92.86 92.88 90.23 90.21 91.94 88.71 84.88 78.36 89.93.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.70 0.71 0.87 0.53 0.68 0.54 0.88 0.89 0.70Acyclic(N4)/cyclic(< = N4), 6.00 5.38 3.72 8.39 5.80 8.05 4.03 2.38 5.19weight ratio__________________________________________________________________________ Example No. 367 368 369 370 371 372 373 374 375 376__________________________________________________________________________Catalyst Type HH HH HH HH HH HH HH HH HH HHCatalyst weight, gm 69.34 69.34 69.34 69.34 69.34 69.34 69.34 69.34 69.34 69.34Pressure, psig 603 604 603 604 603 604 604 604 603 604Temperature, .degree.C. 271 282 260 270 260 281 272 280 272 271Time on organics, hrs. 158 163 182 187 206 211 272 235 254 257.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 4.01 4.31 4.28 4.05 4.11 4.41 4.13 4.11 4.22 4.43DETA/MEA mole ratio 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 5.97Crude product composition, wt. %EDA 1.212 1.778 0.757 0.980 0.861 2.156 1.946 2.350 1.794 1.594MEA 12.554 9.298 20.034 13.105 18.882 8.720 12.941 7.170 13.118 13.362PIP 1.009 1.387 0.734 0.962 0.794 1.385 1.150 1.343 1.147 1.045DETA 37.117 36.552 46.016 38.892 44.565 34.824 39.610 33.663 39.912 38.851AEEA 1.046 0.554 1.888 1.280 1.745 0.521 1.185 0.478 1.195 1.279AEP 1.212 1.598 0.679 0.976 0.784 1.518 1.109 1.669 1.094 1.015HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 2.311 2.549 2.223 2.513 2.187 2.296 2.546 2.452 2.458 2.4961-TETA 11.703 13.076 10.211 11.973 10.178 12.160 12.466 13.106 12.081 12.149DAEP 0.669 0.839 0.209 0.394 0.335 0.916 0.518 1.012 0.454 0.423PEEDA 0.476 0.594 0.174 0.318 0.240 0.634 0.377 0.766 0.348 0.321DPE 0.112 0.468 0.072 0.186 0.150 0.127 0.092 0.123 0.079 0.072AE-TAEA 3.397 4.484 2.580 3.922 2.727 4.290 3.863 4.417 3.624 3.5401-TEPA 7.003 8.450 5.015 7.390 5.407 8.840 7.583 9.218 7.097 6.990AE-DAEP 0.928 0.694 0.198 0.427 0.351 0.189 0.411 0.892 0.342 0.038AE-PEEDA 0.153 0.085 0.045 0.079 0.059 0.132 0.052 0.135 0.036 0.038iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.287 0.093 0.051 0.166 0.042 0.411 0.073 0.390 0.091 0.061BPEA 0.510 0.761 0.054 0.563 0.330 0.822 0.597 0.843 0.577 0.535Others 7.302 7.358 3.390 6.493 3.912 10.339 5.881 9.704 5.473 5.321Conversion, % 64.82 74.69 45.65 63.83 48.59 76.20 64.94 80.41 63.82 62.91DETA conversion, % 38.19 40.86 25.81 36.20 27.88 43.50 36.22 45.35 34.58 34.25Acyclic(N4), wt. % 91.77 89.15 96.47 94.16 94.46 89.61 93.83 89.12 94.28 94.72Acyclic(N5), wt. % 84.70 88.79 95.62 90.16 91.23 89.42 91.00 85.78 91.11 91.63.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.80 0.83 0.62 0.82 0.68 0.91 0.79 0.91 0.76 0.74Acyclic(N4)/cyclic(< = N4), 4.03 3.20 6.65 5.11 5.37 3.16 4.63 3.17 4.66 5.09weight ratio__________________________________________________________________________
TABLE XXXV__________________________________________________________________________ Example No. 377 378 379 380 381 382 383 384 385__________________________________________________________________________Catalyst Type II II II II II II II II IICatalyst 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, gmol/hr/kgcat 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 1.3101-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 0.0001-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 XXXVI__________________________________________________________________________ Example No. 386 387 388 389 390 391 392 393 394__________________________________________________________________________Catalyst Type JJ JJ JJ JJ JJ JJ JJ JJ JJCatalyst weight, gm 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 600Temperature, .degree.C. 270 270 280 260 270 260 280 280 270Time on organics, hrs. 7 26 30.5 50 55 74 79 98.8 123Duration of run, hrs. 2 2 1 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 3.62 3.73 3.53 3.46 3.70 3.56 3.47 3.46 3.40DETA/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 0.294 0.424 0.706 0.273 0.506 0.342 0.979 1.001 0.624MEA 25.314 22.475 18.589 26.092 22.747 25.743 18.317 16.142 21.635PIP 0.421 0.496 0.707 0.266 0.485 0.297 0.712 0.692 0.469DETA 54.036 51.203 48.723 54.115 52.329 54.167 48.580 42.653 47.745AEEA 1.899 2.033 1.670 2.115 2.193 2.258 1.799 1.403 1.963AEP 0.488 0.616 0.869 0.374 0.614 0.438 0.855 0.848 0.588HEP 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 1.5511-TETA 6.203 8.239 9.101 5.680 7.515 6.023 8.740 9.202 7.737DAEP 0.091 0.205 0.282 0.096 0.157 0.110 0.267 0.415 0.216PEEDA 0.093 0.162 0.229 0.076 0.133 0.090 0.209 0.313 0.172DPE 0.048 0.111 0.178 0.076 0.126 0.084 0.220 0.387 0.232AE-TAEA 1.230 1.884 2.347 1.338 1.704 1.006 1.902 2.806 1.8321-TEPA 2.363 3.385 4.197 1.841 2.798 1.882 3.504 5.099 3.159AE-DAEP 0.139 0.145 0.257 0.143 0.273 0.114 0.392 0.812 0.539AE-PEEDA 0.066 0.034 0.101 0.042 0.061 0.024 0.100 0.168 0.078iAE-PEEDA 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 0.035BPEA 0.110 0.211 0.290 0.056 0.110 0.069 0.063 0.209 0.048Others 2.415 3.286 4.610 2.509 3.660 2.432 4.633 8.202 4.835MEA conversion, % 31.77 40.08 50.03 29.37 39.57 30.42 49.72 55.92 40.42DETA conversion, % 13.44 18.87 22.15 12.94 17.39 12.99 20.75 30.77 21.85Acyclic(N4), wt. % 97.01 95.43 94.10 96.54 95.63 96.27 93.80 90.77 93.73Acyclic(N5), wt. % 91.93 92.41 89.53 90.91 88.22 90.67 89.75 83.77 87.68.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.50 0.55 0.63 0.49 0.54 0.42 0.54 0.78 0.57Acyclic(N4)/cyclic(< = N4), 6.61 6.27 4.85 7.78 6.01 7.18 4.65 4.13 5.53weight ratio__________________________________________________________________________ Example No. 395 396 397 398 399 400 401 402 403 404__________________________________________________________________________Catalyst Type JJ JJ JJ JJ JJ JJ JJ JJ JJ JJCatalyst weight, gm 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5Pressure, psig 585 598 598 598 598 598 598 598 598 598Temperature, .degree.C. 271 282 260 270 260 281 272 280 272 271Time on organics, hrs. 158 163 182 187 206 211 272 235 254 257.5Duration of run, hrs. 2 2 2 2 2 2 2 2 2 2MEA SV, gmol/hr/kgcat 2.97 3.69 3.58 3.41 3.41 3.54 3.99 3.53 3.50 3.70DETA/MEA mole ratio 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 5.97Crude product composition, wt. %EDA 0.764 1.129 0.479 0.786 0.509 1.756 1.803 1.993 1.749 1.597MEA 20.571 16.885 25.262 21.504 25.342 18.397 20.631 15.100 20.996 22.350PIP 0.531 0.826 0.351 0.538 0.352 0.865 0.634 0.781 0.638 0.567DETA 47.941 46.768 52.656 48.687 51.138 47.357 46.647 42.162 46.440 48.370AEEA 1.707 1.530 2.132 1.979 2.129 1.620 1.738 1.446 1.730 1.824AEP 0.697 1.034 0.470 0.636 0.432 0.927 0.707 0.935 0.676 0.626HEP 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000TAEA 1.641 1.964 1.408 1.541 1.337 1.743 1.648 1.942 1.596 1.5301-TETA 8.006 9.717 6.641 7.305 6.278 8.432 8.037 9.595 7.922 7.422DAEP 0.239 0.408 0.135 0.174 0.125 0.291 0.359 0.442 0.295 0.232PEEDA 0.186 0.297 0.101 0.138 0.094 0.224 0.234 0.314 0.215 0.169DPE 0.211 0.069 0.110 0.183 0.114 0.089 0.099 0.103 0.182 0.107AE-TAEA 1.858 2.661 1.266 1.659 1.462 2.013 2.165 2.975 2.063 1.9051-TEPA 3.247 5.154 2.314 2.935 2.396 3.688 3.984 5.395 3.860 3.394AE-DAEP 0.401 0.342 0.130 0.223 0.173 0.261 0.335 0.507 0.256 0.234AE-PEEDA 0.057 0.062 0.025 0.068 0.063 0.045 0.076 0.117 0.056 0.042iAE-PEEDA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000AE-DPE 0.053 0.067 0.086 0.211 0.083 0.034 0.229 0.080 0.055 0.040BPEA 0.051 0.390 0.040 0.087 0.037 0.225 0.294 0.465 0.272 0.231Others 4.459 5.997 2.874 5.176 3.565 5.035 6.180 8.307 5.107 4.381MEA conversion, % 42.93 55.07 31.89 40.98 31.07 49.41 44.79 58.84 42.66 39.29DETA conversion, % 20.95 26.04 15.63 20.58 17.33 22.60 25.81 31.71 24.63 31.91Acyclic(N4), wt. % 93.81 93.79 95.88 94.70 95.80 94.40 93.33 93.06 93.21 94.64Acyclic(N5), wt. % 90.08 90.08 92.72 88.64 91.56 90.98 86.82 87.74 90.25 90.67.SIGMA.(N5)/.SIGMA.(N4), weight ratio 0.55 0.70 0.46 0.55 0.53 0.58 0.68 0.77 0.64 0.62Acyclic(N4)/cyclic(< = N4), 5.17 4.43 6.90 5.30 6.82 4.25 4.76 4.48 4.74 5.26weight 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.

Number	Name	Date
2073671	Andrews	Apr 1931
2467205	Gresham et al.	Apr 1949
4036881	Brennan et al.	Jul 1977
4044053	Brennan et al.	Aug 1977
4314083	Ford et al.	Feb 1982
4316840	Ford et al.	Feb 1982
4316841	Ford et al.	Feb 1982
4324917	McConnell	Apr 1982
4362886	Ford et al.	Dec 1982
4394524	Ford et al.	Jul 1983
4399308	Ford et al.	Aug 1983
4448997	Brennan	May 1984
4463193	Johnson et al.	Jul 1984
4503253	Ford et al.	Mar 1985
4521600	Wells et al.	Jun 1985
4524143	Vanderpool	Jun 1985
4540822	Vanderpool	Sep 1985
4547591	Brennan et al.	Oct 1985
4550209	Unvert et al.	Oct 1985
4552961	Herdle	Nov 1985
4555582	Vanderpool	Nov 1985
4560798	Ford et al.	Dec 1985
4578517	Johnson et al.	Mar 1986
4578518	Vanderpool et al.	Mar 1986
4578519	Larken et al.	Mar 1986
4584405	Vanderpool	Apr 1986
4584406	Vanderpool et al.	Apr 1986
4588842	Vanderpool	May 1986
4605770	Ford et al.	Aug 1986
4609761	Watts, Jr. et al.	Sep 1986
4612397	Renken	Sep 1986
4617418	Ford et al.	Oct 1986
4683335	Knifton et al.	Jul 1987
4698427	Vanderpool	Oct 1987
4720588	Turcotte et al.	Jan 1988
4806517	Vanderpool et al.	Feb 1989

Number	Date	Country
0228898	Jul 1987	EPX
0290960	Nov 1988	EPX
78945	May 1985	JPX
236752	Oct 1986	JPX
236753	Oct 1986	JPX

Amines catalysis using metallic phosphate condensation catalysts having a cyclic structure

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