Aminoethylethanolamine producers composition and method for producing same

Abstract

A continuously generated alkyleneamines produces composition comprising, based on 100% of the moles of the composition and exclusive of any MEA and water present,a) about 50 to about 90 mole % AEEA,b) less than about 3 mole % EDA but more than 0.01 mole % EDA,c) less than about 2 mole % DETA but more than 0.01 mole % DETA,d) about 5 to about 18 mole % of the combination of PIP, AEP and HEP,e) about 5 to about 20 mole % of one or more of TETAs and TEPAs,f) less than about 1 mole % of other polyalkylene polyamines,g) a mole ratio of AEEA to the combination of PIP, AEP, HEP, DETA and EDA is greater than about 2.5,h) an AEEA to EDA mole ratio greater than about 22 andi) an AEEA to PIP mole ratio greater than about 7;and a process of manufacturing the same, which comprises feeding hydrogen and MEA to a reaction zone containing a fixed bed of a reductive amination catalyst, wherein the hydrogen comprises about 20 to about 80 mole percent of the feed in the reaction zone, the temperature of the reaction zone is about 120.degree. C. to about 300.degree. C., the pressure of the reaction zone is about 200 to about 1200 psig., the conversion of MEA is about 15 to about 42 weight percent, and recovering said producers composition from the reaction zone.

Description

RELATED APPLICATIONS

The following commonly assigned applications, filed on even date herewith:

Ser. No. 07/102,929; Ser. No. 07/102,930; Ser. No. 07/102,927; and Ser. No. 07/102,928.

BRIEF DESCRIPTION OF THE INVENTION

The invention concerns an alkyleneamines producers composition exceptionally rich in aminoethylethanolamine (AEEA) and the method for forming it.

BACKGROUND TO THE INVENTION

A significant portion of the ethylenediamine (EDA) made commercially is by the continuous reaction of monoethanolamine (MEA) and ammonia in the presence of hydrogen over a fixed bed reductive amination catalyst. The reaction unavoidably generates a variety of polyalkylene polyamines as well. Illustrative of many of them are the following:

AEEA--N-(2-aminoethyl)ethanolamine HEP--N-(2-hydroxyethyl)piperazine DETA--Diethylenetriamine AEP--N-(2-aminoethyl)piperazine TETA--Triethylenetetramine TEPA--Tetraethylenepentamine PEHA--Pentaethylenehexamine TETA Isomers: NTEA--Nitrilotrisethylamine TETA--Triethylenetetramine DiAEP--Diaminoethylpiperazine PEEDA--Piperazinoethylethylenediamine TEPA Isomers: AETETA--4-Aminoethyltriethylenetetramine TEPA--Tetraethylenepentamine AEPEEDA--Aminoethylpiperazinoethylethylenediamine PEDETA--Piperazinoethyldiethylenetriamine

Gibson, U.S. Pat. No. 4,400,539, patented Aug. 23, 1983, describes such a process for the manufacture of ethylenediamine. The patent describes a continuous process involving the reductive amination of MEA. A further elaboration of the process of the Gibson patent is described in Winters, U.S. Pat. No. 4,404,405, patented Sept. 13, 1983. The Gibson and Winters patents characterize the relative commercial values attributed to ethylenediamine and piperazine. The direction which the art has been moving in recent years has been away from piperazine towards a more favored product, EDA.

The compositions generated by that reaction are dependent upon a number of factors such as the selection of catalyst for carrying out the reaction, the ratio of reactants, the temperature, the pressure, reactant flow velocity through the catalyst zone, the shape and form of the catalyst, the presence and absence of other reactants such as water, and the like considerations. There are a wide variety of reductive amination catalysts for this reaction. Typically, they are viewed as hydrogenation catalysts. The most prevalent of them utilize nickel as an important ingredient. Raney nickel has for years been viewed as a good hydrogenation catalyst. In recent years, nickel in combination with other metals has grown to be a favored catalyst for effecting the reductive amination reaction.

An excellent survey of that process and the alkyleneamines compositions generated thereby can be found in Barnes et al., Ind. Eng. Chem. Prod. Res. Dev. 1981, 20, 399-407. Table II, at page 402, lists a variety of patent examples and the disclosed products of MEA ammonolysis.

According to Barnes et al.

"The apparently simple reaction of NH.sub.3 and MEA to yield EDA is deceptive, for several catalytic steps are involved, and a number of side reactions occur."

The variety of products generated by that reaction reflects the complexity of the chemistry involved.

Until recently, AEEA was viewed to be an unwanted by-product of a number of processes (including reductive amination) for the manufacture of alkyleneamines. It has long been considered to be a precursor to PIP. See U.S. Pat. No. 2,479,657 and 3,383,417. The value of AEEA has risen considerably in recent years because significant commercial uses have evolved for it. Because the commercial processes have been designed to produce EDA and minimize the formation of PIP, owing to the limited demand for PIP, little is known about the manipulation of the commercial processes to generate larger amounts of AEEA. There are a few patents directed to the manufacture of AEEA. They do not rely on the reaction of MEA and ammonia.

Lichtenwalter, U.S. Pat. No. 3,383,417, patented May 14, 1968, describes a process for the manufacture of aminoethylethanolamine (AEEA) by the reaction of monoethanolamine (MEA) in the absence of added ammonia with a catalyst containing a major amount of nickel, copper and a minor amount of chromium oxide, manganese oxide, molybdenum oxide and/or thorium oxide at a temperature of 150.degree. C. to 250.degree. C. and a pressure of 2000 to 4000 psig. correlated so as to provide for the total conversion of about 10% to 30% of the monoethanolamine. The reaction conditions include a pressure of about 2,000 to 4,000 psig., composed of at least 80% of hydrogen partial pressure. A critical factor of the invention is to limit the degree of conversion of the MEA to no more than 30%. The examples of the patent demonstrate that "only a minor amount of aminoethylethanolamine was obtained with conversion about 40%". As the MEA conversion proceeds above 30%, the AEEA yield becomes minor in the reaction product relative to the yield of piperazine (PIP). The compositions (in mole percents) made by this process are set forth in Tables 1 and 2 of the patent and are set out in the following table:

______________________________________ AEEA PIP + AEP + HEP + EDA +AEEA DETA EDA PIP AEP HEP DETA______________________________________75.5 0.7 5.8 15.7 1.4 0.9 3.0875.5 0.4 11.9 11.6 0.3 0.3 3.0863.3 0.7 8.5 24.0 2.6 0.7 1.7350.5 0.6 8.6 30.3 6.6 3.2 1.0231.0 0.8 2.3 41.8 15.3 8.8 0.4528.6 3.1 10.4 37.5 9.6 10.7 0.4047.4 0.9 10.7 25.8 11.2 3.9 0.9024.1 -- 8.4 24.1 8.4 3.6 0.5447.8 1.7 6.1 31.0 8.1 5.2 0.9245.6 1.1 8.1 28.8 8.9 7.5 0.8429.6 -- 7.8 41.2 11.9 9.5 0.4925.7 1.0 7.6 43.8 12.6 9.3 0.3512.5 0.9 5.6 51.5 13.4 10.2 0.18______________________________________

Lichtenwalter demonstrates the effects of operating under severe conditions of the combination of high temperature and pressure. The reaction of MEA with itself involves the condensation of amino group with hydroxyl group. The production of EDA reflects the cleavage of hydroxylethyl from AEEA, an apparent deficiency in the reaction. The more EDA formed, the more inefficient is the reaction. The degree of formation of PIP, AEP and HEP demonstrates the extent that AEEA is cyclized. The condensation of MEA with itself ("intramolecular condensation") can be pushed to primarily form cyclic amines. The formation of EDA is not part of the scheme of the condensation reaction, yet in the reductive ammonolysis reaction, EDA is an unavoidable impurity.

Ford, et al., U.S. Pat. No. 4,560,798, patented Dec. 24, 1985, utilizes a process in which the reactant, MEA, is vaporized and fed to the catalyst in the vapor state. The catalyst employed is not a reductive amination catalyst as in U.S. Pat. No. 3,383,417, but rather a specific rare earth or strontium metal hydrogen phosphorus-containing compound. The reaction is carried out at 50 to 400 psig. and at a temperature of from 175.degree. C. to 275.degree. C. No hydrogen is provided in the feed. In addition, ammonia is not included as a reactant. According to the data characterized in Table 1, at Column 6 of the patent, it is quite evident that as temperature is raised the percent conversion also goes up and the selectivity to AEEA goes down materially.

A major distinction between the process of Lichtenwalter and Ford, et al. is the presence of EDA as a significant product in Lichtenwalter's process and its apparent absence from the Ford, et al. process. This results in the Ford, et al. process producing large quantities of HEDETA rather than the DETA and EDA generated by the Lichtenwalter process. Lichtenwalter fails to suggest the production of HEDETA.

Lichtenberger, et al., U.S. Pat. No. 3,068,290, patented Dec. 11, 1962, referred to in Table II of Barnes et al., supra, describes the batch manufacture of EDA by the reaction of MEA and ammonia in the absence of hydrogen in the presence of Raney nickel in an autoclave, and depicts in Example III, the following composition, exclusive of MEA and water:

______________________________________ MoleProduct Weight (g.) Moles Mole % Ratio______________________________________EDA 260 4.48 56PIP 70 0.81 10DETA 103 1.0 13AEEA 138 1.33 17TETAS + 48 .33 4VARIOUS AMINESAEEA/EDA .30AEEA/DETA 1.31______________________________________

Because the various amines are unknown compositions, they were treated as TETAS for the purposes of this characterization.

Johansson, et al., U.S. Pat. No. 3,766,184, patented Oct. 16, 1973, criticizes the commercial applicability of the catalyst, and hence the process, of Lichtenberger, et al., see the discussion at col. 2, lines 18 to col. 3, line 5. However, a point not raised by Johansson, et al. is the absence of hydrogen in the process of Lichtenberger, et al. The absence of hydrogen makes the process of Example III of Lichtenberger, et al. not readily reproducible, if ever reproducible, in a continuous process.

It is fairly well appreciated in the reductive amination art that the reductive amination catalyst must be first reduced before effecting the reaction, and then continuously reduced during the course of the reaction in order to keep the catalyst active and functioning. The degree of this reduction will determine the catalyst's productivity and selectivity to products. In the case of Lichtenberger, et al.'s Example III, the Raney nickel had to have been reduced with hydrogen prior to use. It is that level of hydrogenation that will sustain the reaction. As the level of the catalyst's surface becomes depleted of bound hydrogen, the catalysts activity is reduced and its composition is changed. Eventually the catalyst will become depleted of its bound hydrogen, and when that occurs, the reaction terminates. But in the course of the reaction, the composition of the reaction product changes. What is found in the reactor is a composite composition that changes over the course of the limited life of the catalyst.

Moss, et al., U.S. Pat. No. 3,151,115, patented Sept. 29, 1964, describe a process for the "maximum recovery of piperazine and N-aminoethylpiperazine," obtained at a MEA conversion "of about 75 to 95%", and depict the following table in column 6:

TABLE______________________________________Data From U.S. Pat. No. 3,151,115 1 2 3 4.sup.1 5.sup.1______________________________________Reactor Temp., .degree.C. 199 198 198 223 227Hydrogen rate: SCFH 800 800 800 800 800Reaction press., psig 2,800 2,800 2,800 2,800 2,800Feed rates, gal./hr:NH.sub.3 (anhydrous) 94 70 47 80 80Monoethanolamine (MEA) 35.5 25.5 16 158 158Space velocity, 6.2 4.5 3.0 3.1 3.1g./hr. ml. cat.Conversion of MEA, 29.3 39.8 53.8 71.4 75.4percentYields (molar), percent:Ethylene diamine (EDA) 41.3 38.5 36.2 12.0 15.0Piperazine (PIP) 13.7 18.7 23.2 47.6 58.0Diethylenetriamine (DETA) 7.1 7.6 9.3 9.0 3.3N-aminoethylpiperazine (AEP) 2.1 3.0 3.0 15.0 17.5Aminoethylethanolamine 23.3 18.4 13.2 -- --(AEEA)Hydroxyethylpiperazine (HEP) 0.5 2.2 3.2 6.0 3.5Residue 12.0 11.6 11.9 10.4 2.7PIP + AEP 15.8 21.7 26.2 62.6 75.5______________________________________ .sup.1 Also used 140 gal. water/hr. in feed

The following mole ratios were determined from the data in column 1 of the table from Moss, et al.:

AEEA/EDA mole ratio: 0.56 AEEA/DETA mole ratio: 3.28 EDA/PIP+AEP+HEP mole ratio: 2.53 AEEA/PIP+AEP+HEP mole ratio: 1.43

The process of the Moss, et al. patent employs high pressures and through the loss of conversion and temperature reduction, coupled with a few other variable changes, generated a relatively high yield of AEEA in a non-preferred mode of operation. However, in doing so, the patentee generated a large amount of residues (presumed to be TETAs, TEPAs and other higher polyamines), and a small amount of DETA, without a clue to how one could avoid that result. In the case of Moss, et al., there is described an example which utilizes costly high pressures combined with low conversion to produce a composition rich in AEEA and also rich in residues, and poor in DETA, without the capacity of lowering the residues content and enriching the DETA content.

It would be desirable to have continuously produced compositions generated by the self-condensation reaction of MEA over a fixed bed of a reductive amination catalyst under commercial conditions that are rich in AEEA, and that are not disproportionately high in EDA, DETA, PIP and other cyclics.

It would be desirable to have a process which increases one's ability to generate with commercially functional catalysts the manufacture of AEEA without generating large amounts of EDA, DETA and cyclic alkylenepolyamine products. In addition, it is also desirable to have a process which is dedicated to the manufacture of AEEA over a reductive amination catalyst without the need of using costly and stringent process conditions as exemplified in U.S. Pat. No. 3,383,417. It would be most desirable to have the ability to generate AEEA at low pressures such as are typically employed in the condensation of MEA over an acid condensation catalyst as exemplified in U.S. Pat. No. 4,560,798, but to be able to use instead a reductive amination catalyst. These features are provided by the process of this invention.

THE INVENTION

The invention is directed to a continuously generated alkyleneamines producers composition comprising, based on 100% of the moles of the composition and exclusive of any MEA and water present,

a) about 50 to about 90 mole % AEEA, preferably about 60 to about 80 mole % AEEA, and most preferably about 65 to about 80 mole % AEEA, b) less than about 3 mole % EDA but more than 0.01 mole % EDA, c) less than about 2 mole % DETA but more than 0.01 mole % DETA, d) about 5 to about 18 mole % of the combination of PIP, AEP and HEP, preferably about 5 to about 15 mole % of the combination of PIP, AEP and HEP, e) about 5 to about 20 mole % of one or more of TETAs and TEPAs, preferably about 5 to about 17 mole % of one or more of TETAs and TEPAs, f) less than about 1 mole % of other polyalkylene polyamines, g) a mole ratio of AEEA to the combination of PIP, AEP, HEP, DETA and EDA is greater than about 2.5, h) an AEEA to EDA mole ratio greater than about 22, and i) an AEEA to PIP mole ratio greater than about 7.

The invention is also directed to the process of manufacturing the alkyleneamines producers composition comprising, based on 100% of the moles of the composition and exclusive of any MEA and water present,

a) about 50 to about 90 mole % AEEA, preferably about 60 to about 80 mole % AEEA, and most preferably about 65 to about 80 mole % AEEA, b) less than about 3 mole % EDA but more than 0.01 mole % EDA, c) less than about 2 mole % DETA but more than 0.01 mole % DETA, d) about 5 to about 18 mole % of the combination of PIP, AEP and HEP, preferably about 5 to about 15 mole % of the combination of PIP, AEP and HEP, e) about 5 to about 20 mole % of one or more of TETAs and TEPAs, preferably about 5 to about 17 mole % of one or more of TETAs and TEPAs, f) less than about 1 mole % of other polyalkylene polyamines, g) a mole ratio of AEEA to the combination of PIP, AEP, HEP, DETA and EDA is greater than about 2.5, h) an AEEA to EDA mole ratio greater than about 22, and i) an AEEA to PIP mole ratio greater than about 7. which comprises feeding hydrogen and MEA to a reaction zone containing a fixed bed of a reductive amination catalyst, wherein the hydrogen comprises about 20 to about 80 mole percent of the feed in the reaction zone, the temperature of the reaction zone is about 120.degree. C. to about 300.degree. C., the pressure of the reaction zone is about 200 to about 1200 psig., the conversion of MEA is about 16 to about 42 weight percent, and recovering said producers composition from the reaction zone.

DETAILS OF THE INVENTION

AEEA has developed into a very useful commercial product for a variety of applications. There is lacking a commercial process for the manufacture of AEEA as a principal product of reaction. There is a need for the ability to commercially generate larger production quantities of AEEA and that is the direction of this invention.

It is an objective of this invention to effect a reaction of MEA in the presence of hydrogen to produce in a continuous manner a reaction product mixture, termed herein an "alkyleneamines producers composition," in which AEEA is the principal product of the reaction. It is a particular objective of this invention to effect the continuous reaction of MEA with hydrogen over a solid reductive amination catalyst to produce AEEA as the principal product of the reaction. It is also an objective of this invention to effect the reaction of MEA and hydrogen over a fixed bed of a solid reductive amination catalyst to produce AEEA as the only principal product of the reaction.

The alkyleneamines producer compositions of the invention can be subjected to conventional separations techniques for recovering the individual components of the compositions. Illustrations of such techniques can be found in Gibson, Winters and Moss, et al., supra.

In the foregoing description of the compositions of the invention, the TETAs and the TEPAs include the variety of hydroxyethyl components generated in the reactions herein set forth, such as hydroxyethyl DETA and hydroxyethyl TETAs. Thus for the purpose of this invention, the TETAs and TEPAs embraced by the specification and the claims include this variety of hydroxyethyl components.

The process of this invention is distinctive insofar as it achieves the generation of high concentrations of AEEA 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 AEEA at relatively low pressures thereby effecting a substantial energy saving in the manufacture of AEEA as compared to that described in U.S. Pat. No. 3,383,417. As indicated above, the pressure for carrying out the process for this invention is less than about 1200 psig. (8274 kPa.), however, it is preferred that the pressure used in practicing the process is less than about 1,000 psig. (6895 kPa.), most preferably less than about 800 psig. (5516 kPa.). In the preferred operation of the process the pressure employed in carrying out the process is above about 200 psig. (1379 kPa.). In the usual practice of this invention, the pressure will typically range between about 300 psig. (2068.5 kPa.) to about 800 psig.

The process is typically carried out at a temperature between about 120.degree. C. (248.degree. F.) and about 300.degree. C. (572.degree. F.), preferably from about 150.degree. C. (302.degree. F.) and about 250.degree. C. (482.degree. F.).

The process of this invention is effected by feeding to a tubular reactor a stream of the reactant mixture comprising MEA and hydrogen, where hydrogen comprises about 20 to about 80 mole percent of the feed, to the reaction zone therein containing a fixed bed of the reductive amination catalyst. Water may be provided in the feed up to about 20 weight % of the MEA. The reaction zone is defined as a zone in the reactor containing the catalyst where the reaction is initiated, that is, where there is a self-condensation reaction going on between the MEA. The reaction zone ends when the self-condensation reaction ceases or the feed stream is out of contact with the catalyst, whichever is the later to occur in time.

The feed stream may be liquid, supercritical fluid or gaseous. The reaction product stream taken from the reaction zone may be liquid, supercritical fluid or gaseous. It is not necessary that the feed stream and the reaction product stream be in the same physical state. For example, the reactant stream may be gaseous and the reaction product stream liquid, and vice versa.

The tubular reactor design is not narrowly critical. The feed thereto may be upflowing or downflowing. Tubular reactors which provide the most favorable plug flow conditions are favored. The tubular reactor may be straight or curved. Design features in the reactor which optimize plug flow in the reactor may be employed. The process of this invention benefits significantly from good plug flow of the reactants and the reaction products through the reactor.

The catalysts which may be employed in the practice of this invention are those which have previously been employed for the condensation reaction of an alkanolamine and ammonia. There is an abundance of art which cite the type of catalysts which may be employed in the practice of this invention. Illustrative art which depict catalysts suitable for use in the practice of this invention are the following:

U.S. Pat. No. 4,560,798 patented Dec. 24, 1985

U.S. Pat. No. 4,463,193 patented July 31, 1984

U.S. Pat. No. 4,362,886 patented Dec. 7, 1982

U.S. Pat. No. 4,316,841 patented Feb. 23, 1982

U.S. Pat. No. 4,316,840 patented Feb. 23, 1982

U.S. Pat. No. 4,314,083 patented Feb. 2, 1982

U.S. Pat. No. 4,503,253 patented Mar. 5, 1985

U.S. Pat. No. 4,578,517 patented Mar. 25, 1986

U.S. Pat. No. 4,521,600 patented June 4, 1985

U.S. Pat. No. 4,394,524 patented July 19, 1983

U.S. Pat. No. 4,555,582 patented Nov. 26, 1985

U.S. Pat. No. 4,584,406 patented Apr. 22, 1986

U.S. Pat. No. 4,588,842 patented May 13, 1986

U.S. Pat. No. 4,550,209 patented Oct. 29, 1985

U.S. Pat. No. 4,552,961 patented Nov. 12, 1985

U.S. Pat. No. 4,588,842 patented May 13, 1986

Japanese Patent Appl. No. 262713/85 Laid-open No. 130260/86 filed Nov. 25, 1985

U.S. Pat. No. 4,123,462 patented Oct. 31, 1978

U.S. Pat. No. 4,111,840 patented Sept. 5, 1978

EPC Ser. No. 83113181.8 filed Dec. 28, 1983

U.S. Pat. No. 4,568,746 patented Feb. 4, 1986

U.S. Pat. No. 4,552,961 patented Nov. 12, 1985

U.S. Pat. No. 4,647,701 patented Mar. 3, 1987

U.S. Pat. No. 4,625,030 patented Nov. 25, 1986.

The reductive amination catalyst is a classical hydrogenation catalyst. As is the case with the preponderance of the hydrogenation catalysts they typically contain such metals as nickel, rhodium, rhenium, zinc, palladium, platinum, and the like. A particularly desirable reductive amination catalyst is based on the presence at the catalyst's surfaces of nickel.

Of particular interest as a reductive amination catalyst is a potentiated catalyst comprising nickel on various support materials including a-alumina, silica, silica-alumina, kieselguhr, diatomaceous earth and silica-titania which are active and selective in the conversion of various alkane derivatives to amine products. The potentiation of the catalysts is provided by the incorporation with the nickel of a potentiating amount of a metal component of one or more of iridium and platinum. Iridium is the preferred potentiating agent.

These potentiated catalysts comprising nickel impregnated or coated together with a potentiating agent on a support material selected from alumina, silica, silica-alumina, kieselguhr, diatomaceous earth, and silica-titania, wherein the mole ratio of the nickel to total potentiating agent is in the range of from 1:1 or 2:1 to about 30:1 and the total nickel metal and potentiating agent present is in the range of about 1 to 30%, say about 3-30% by weight of the support.

The potentiated nickel catalyst are made by (i) impregnating a mixture of metals comprising the potentiating agent iridium and nickel on a support material selected from the group consisting of alumina, silica, silica-alumina, kieselguhr, diatomaceous earth and silica-titania; and (ii) activating said catalyst by heating the catalyst in the presence of hydrogen at a temperature in the range of about 200-600 C. for a period of about 45 minutes to about 4 hours.

The support materials for the potentiated catalysts which have been found to produce the most active and selective amination catalysts are those supports which are composed of silica, silica-alumina, alumina, silica-titania, kieselguhr or diatomaceous earth. Most of these support materials are well-known in the art and are commercially available.

Support materials are not equivalent in their ability to form active potentiated nickel catalysts. For example, carbon-supported, potentiated nickel catalysts using CXC carbon from National Carbon Company, even with large surface areas, have not shown appreciable catalytic activity in amination reactions.

Even the aforementioned support materials which have yielded active potentiated nickel catalysts are not equivalent. Those supports which form more active catalysts yield optimum amination conversions at less severe reaction conditions, e.g., lower reaction temperatures. Therefore, although all supports tested within the group indicated above show some catalytic activity in the amination reaction, some supports within a general type have not been considered as having strong commercial promise because more extreme reaction conditions, such as higher reaction temperatures, must be used to obtain satisfactory conversions.

The actual effectiveness of a material as a support in a potentiated nickel catalyst is generally not predictable in advance. However, among the general types of supports indicated above that have been found active, there appears to be some relationship between catalytic activity and the amount of the surface area of the particular support materials.

Specific examples of some of the more active support materials for the potentiated nickel catalysts are listed in the table below:

TABLE 1______________________________________ Surface AreaSupport General Type m.sup.2 /gm______________________________________Girdler T869 Silica-alumina about 60Girdler T1571 Silica-alumina about 150Girdler T372 alpha-alumina about 40Girdler T373 Silica-alumina 2-3Girdler K302 Silica-alumina about 250Girdler T2085 Silica-alumina about 113Girdler K10 Silica-alumina about 268Girdler T2045 KieselguhrNorton LA 4102 alpha-alumina 1Johns-Manville Diatomaceous silica 10-15Type IIIGrace 980-13 Silica alumina about 375Grace 980-25 Silica alumina about 375Laboratory Silica titania about 75-115 (SiO.sub.2 /TiO.sub.2 Mole Ratio 9:1 to 1:9)______________________________________

In the amination reactions of the present invention, supports having a surface area of 1 m.sup.2 /gm or greater are preferred.

The support materials which may be used in making the catalyst may be of any convenient shape or size. The shape of the support usually will depend upon the shape required in the particular apparatus used to perform the catalyst conversion reaction. Catalysts can be made on support materials in the form of powders, spherical pellets and extruded strips. Impregnated spherical pellets ranging in diameter from 1/8 inch to 3/16 inch and extruded strips of a cylindrical-type shape ranging from 1/32 inch to 1/2 inch in length are typical of those which can be used as supports.

The particular method of impregnating or coating the nickel and potentiating agent onto the support material has an insignificant effect on the activity or selectivity of the final catalyst in amination processes; however, impregnated catalysts generally perform better than coated catalysts. The amount of metal provided on the support material and the nature of the support itself can affect or vary the catalytic activity and/or selectivity.

One technique for impregnating the nickel and potentiating agent onto the support is to use a solution of salts of the metals as a vehicle.

Various organic and inorganic nickel and potentiating agent salts may be used in impregnation solutions. Examples of suitable nickel-containing salts are anhydrous and hydrated nickelous nitrate hydrate: [Ni(NO.sub.3).sub.2 6H.sub.2 O] and nickel acetonyl acetate [Ni(C.sub.5 H.sub.7 O.sub.2).sub.2 ]. Suitable potentiating agent salts for use in the impregnating solution are platinum (II) chloride, platinum II acetylacetonate, iridium (III) chloride, iridium (III) acetylacetonate. In some cases, it is advantageous to heat the solvent liquid to bring the metal salts into solution.

The salt solution should be prepared by considering two factors. The first concerns the amount of total metal desired to be impregnated on a specific quantity of support. The second factor concerns the relative atom ratio of nickel to potentiating agent. Both factors have been found to affect the final properties of the catalyst.

Some active catalysts have been found to be those in which the nickel to potentiating agent atom ratio is between 1:1 and 30:1. In most cases, maximum activity occurs with this ratio being between about 5:1 and 20:1. In preparing the catalyst, this atom ratio is obtained by predetermining the corresponding relative proportions of the metal salts to be present in the impregnation solution.

The total metal to be impregnated onto the support also has an effect on the activity of the catalyst. The potentiated nickel catalysts typically contain a total nickel plus potentiating agent metal content in the range of about 1 or 3 to 30%, e.g., about 5 to 20%, by weight of the support material.

Where relatively large amounts of metal are to be impregnated on supports, a single impregnation step may not be sufficient. Although an impregnation solution may be prepared with the minimum amount of solvent required to dissolve the metal salts, the total amount of the impregnation solution may be greater than that which the support material can absorb.

In such case, a portion of the impregnation solution less than the maximum absorption amount is used to initially contact the support material. After contacting, the support material is dried and then contacted with an additional amount of impregnation solution. The sequential steps of contacting with solution and drying are continued until all of the impregnation solution is used. A typical drying step can comprise heating the impregnated support to a temperature of 120.degree. C. for several hours. Evacuation drying may also be used, where the support is cooled under reduced pressure.

It is also advantageous to dry the support material prior to impregnation in order to ensure that the support will take up as much of the solution as possible. This pre-drying step also enables the metal to permeate more deeply into the support during impregnation. The penetration of the metal into the support may be further increased by techniques known to those skilled in the art such as by increasing the time the support is in contact with the solution. Other impregnation techniques are well known in the art and may be utilized in the present invention.

Another technique which can be used is often characterized as a "sugar coating" technique where the metal is predominantly present on the outer surface of the support material. The sugar coating technique differs from the impregnation process described above by the addition of a precipitant at the time the impregnating salt solution is in contact with the support material. The precipitant converts the metal salt solution into a slurry. This impregnating vehicle reduces the penetration of the salts beyond the surface of the support material. The slurry in contact with the support material is then evaporated to dryness leaving the metal adhering predominantly to the support surface.

After the support material is impregnated with the desired amount of nickel and potentiating agent, it is completely dried and then activated by a reduction step.

The drying step to be used is any technique which sufficiently evaporates the volatile constituents of the impregnating solution. The drying step may comprise heating the catalyst to a temperature of about 120.degree. C. The drying may be done under an inert atmosphere such as nitrogen, and the catalyst may be cooled under reduced pressure.

The catalyst is then activated by a suitable step wherein the impregnated metal is converted into a catalytically-active form. This activation may include alloy formation, proper phase orientation of the metals and/or an adjustment in the oxidation level of the metals. An activation step may include a typical reduction process.

The preferred activation of the catalyst is to contact it with a hydrogen atmosphere which is fed over the catalyst at an elevated temperature in the order of about 200.degree. to about 600.degree. C. for periods of from about 45 minutes to about 4 hours. The specific conditions for reduction are dependent upon the particular catalyst composition being activated.

Prior to the activation step, the catalyst may be optionally calcined. In a preferred calcining step, the catalyst is heated to temperatures in the range of about 300.degree. to 550.degree. C. for one minute to about 3 hours or more. It is preferred that the calcining be carried out in air. The drying step referred to above may be replaced by the calcining step or activating step.

The potentiated nickel catalysts include catalysts which contain various other metals in admixture with the nickel and potentiating agent which do not detrimentally affect catalytic properties. These additional metals, in certain amination processes, may actually improve selectivity and activity of the basic potentiated nickel catalyst. Certain of these metals may extend the activity life and other physical properties of the catalyst. Examples of additional metal components include lanthanum, boron, magnesium, lithium, sodium, potassium, rubidium, cesium, cerium, iron, ruthenium, copper, silver, zinc, cobalt, palladium, titanium, manganese, rhodium, and rhenium. In order to prepare such catalysts, salts of these additional metals are added in suitable amounts to the impregnation solution containing the nickel and potentiating agent. The amount of such additional metal components, based on nickel and expressed as an atomic ratio, is about 0.001:1 to 1:1, frequently about 0.01:1 to 0.5:1. Particularly preferred catalysts comprise nickel, iridium and rhenium. In these catalysts, the rhenium is generally provided in an atomic ratio of iridium of about 10:1 to 1:10.

In the case of the nickel-rehenium catalysts, the preferred mole ratio of the nickel to the rhenium is the range of from 2:1 to about 30:1 and the total nickel and rhenium metal present is in the range of 3 to 30 percent by weight of the support. Such catalysts can be prepared by the methods taught in U.S. Pat. Nos. 4,111,840 and 4,123,462, the pertinent parts of which are incorporated herein by reference. Basically, such catalysts are solid catalysts wherein the nickel and rhenium metals are supported on certain catalyst support materials.

The nickel-rhenium catalyst can contain various other metals in admixture with the nickel and rhenium which do not detrimentally affect the catalytic properties of catalysts containing nickel and rhenium as the only impregnated metals. These additional metals can actually improve selectivity and activity of the basic Ni--Re catalyst. Certain of these metals can extend the activity life and other physical properties of the Ni--Re catalyst. Examples of catalysts containing additional metal components include Ni--Re--La, Ni--Re--Ca, Ni--Re--Mg, Ni--Re--Sr, Ni--Re--Li, Ni--Re--K, Ni--Re--Ba, Ni--Re--Ce, Ni--Re--W, Ni--Re--Fe, Ni--Re--Ru, Ni--Re--Cu, Ni--Re--Ag, Ni--Re--Zn, Ni--Re--Co, Ni--Re--U, Ni--Re--Ti, Ni--Re--B and Ni--Re--Mn.

The amount of Ni--Re catalyst present in the process depends on many variables including the relative proportions of the reactants, reaction conditions and the degree of conversion and selectivity desired. Moreover, the amount of catalyst will depend also on the nature of the catalyst itself, e.g., its metal loading and activity and age. The catalyst must be present in the reaction zone in sufficient catalytic amount to enable the desired reaction to occur. This is also true for any of the catalysts useful in the invention process.

Other preferred reduction amination catalysts are catalyst composed of rhenium, nickel and boron impregnated on a support material selected from the group consisting of aluminas (e.g., alpha), silicas, silica-aluminas, kieselguhrs or diatomaceous earths and silica-titanias, wherein the ratio of nickel to boron to rhenium is in the range of from about 2:2:1 to about 30:30:1 and the total nickel, boron and rhenium present is in the range of about 3 to about 30 percent by weight of the support material.

The most preferred mode of the catalyst is a reductive amination catalyst which has a silica support marketed under the mark T-869.sup.R by United Catalyst Incorporated. The best mode of the catalyst is obtained from the United Catalyst Incorporated. It is believed that the catalyst is prepared by impregnating the T-869.sup.R catalyst support with an aqueous solution containing nickel nitrate, ammonium perrhenate and boric acid in a metal composition of 66 percent of nickel, 19.6 percent of rhenium and 14.4 percent of boron. Following the impregnation, it is calcined at 330.degree. C. for 2.5 hours. Then it is impregnated a second time with the same solution and calcined again under the same conditions for the same length of time. Thereafter, it is impregnated a third time to reach a 12 percent total metal loading. It is then calcined at 330.degree. C. for 2.5 hours. Then it is reduced under a hydrogen atmosphere at a temperature of 332.degree. to 337.degree. C. for 16 hours. Following the reduction step it is stabilized at 60.degree. C. for 30 to 40 hours.

Examples of other useful reductive amination catalysts are the rhodium atom-containing catalysts of U.S. Pat. No. 4,322,530, the copper-rhenium catalysts of U.S. Pat. No. 4,206,149, the nickel-cobalt-iron catalysts of U.S. Pat. No. 3,766,184, the cobalt-nickel-copper-containing aluminum oxide or silicon dioxide support catalyst of U.S. Pat. No. 4,014,933 and the catalysts containing copper oxide or copper hydroxide, nickel oxide or nickel hydroxide, and, optionally, an oxide or a hydroxide of a Group IIA metal of U.S. Pat. No. 4,409,399--the pertinent parts of such patents are incorporated herein by reference. U.S. Pat. No. 4,209,424 (the pertinent parts of which are incorporated herein by reference) teaches an amination catalyst which has at least one active metal from the group of transition metals consisting of nickel, cobalt and copper, uniformly combined with a refractory microporous substance.

The pertinent parts of U.S. Pat. No. 4,568,746 are incorporated herein by reference. This patent discloses a process for the production of an amine composition having a high ratio of diethylenetriamine to piperazine which comprises maintaining ethylenediamine in the presence of a nickel, cobalt or rhodium catalyst, wherein the metal is present on the surface of the catalyst in a polyatomic form, and at a temperature between about 170.degree. to about 210.degree. C. sufficient to convert less than about 35 percent of the ethylenediamine feed. The catalyst of U.S. Pat. No. 4,568,746 are nickel, cobalt or rhodium catalysts which can be relatively pure metal catalysts or catalysts that have been modified by the addition of molybdenum, chromium, iron or other transition metals in varying amounts. The catalysts can be in a massive form or they can be supported on a carrier such as the preferred silica or alumina carriers wherein the metal is present on the surface of the catalyst in a polyatomic form. Preferred catalysts are Raney nickel or Raney cobalt or a Ni/Re/B on silica catalyst prepared as described in U.S. Pat. No. 4,123,462. The catalyst charge, as a weight percent of the total charge, is not narrowly critical, although a charge of about 10 weight present is preferred for the reaction temperature and times taught in U.S. Pat. No. 4,568,746.

The pertinent portions of U.S. Pat. No. 4,625,030 are incorporated herein by reference. This patent discloses the potentiated nickel reductive amination catalysts discussed above.

The conditions of the reaction are not narrowly limited. As pointed out above, the reaction temperature and pressure is to be kept within about the ranges set forth above. The invention is not limited to a confining set of conditions. The reactants can be fed as a stream, typically continuously, to the bed of the catalyst. The catalyst is usually a fixed bed of solid particles (pellets, tablets, extrudates, spheres, etc.) which comprise the catalyst deposited on a solid, relatively inert support, such as those described above. The reaction occurs in the bed and thus the bed defines the reaction zone. The effluent from the bed or the reaction zone is also a stream comprising the unreacted components of the feed stream and the principal reaction product, AEEA, plus a number of other amine compounds enumerated herein. The TETAs and TEPAs comprise the various isomeric triethylenetetramines and tetraethylenepentamines.

The following examples are intended for the purpose of illustrating this invention and not for the purpose of limiting it.

EXAMPLES

The reactor used in the examples was a 74.75 inch-long Type 316 stainless steel medium pressure tube of 0.688 inch i.d. and 1.0 inch o.d. The temperature in the reaction zone was measured by three thermocouples evenly distributed in the reaction zone and placed in a 1/8 inch o.d. thermowell located in the center of the tube. Two hundred grams of catalyst containing 6.1 wt. % nickel, 4.5 wt. % rhenium and 1.9 wt. % boron were charged to said reactor and held therein on a stainless steel screen at about 4 inches from the bottom of the tube. The free volume remaining in the tube was filled with an inert material of similar size to the catalyst.

Heating was supplied through the wall of the tube (when necessary) by three individually controlled heat tapes.

The process was operated according to the conditions set forth in the tables below for each of the enumerated examples. The hydrogen gas was preheated alone and then mixed with MEA. This was done by feeding the hydrogen gas through a preheater and mixed with MEA which had also been pumped to the system and passed through a preheater. This mixture then passed through another preheater prior to entering the reaction zone.

The reaction mixture was passed through the reaction zone in a downflow fashion. The pressure in the reaction zone was controlled by a motor valve at the outlet of the reactor. After leaving the reaction zone the pressure of the stream was reduced from that of the reaction zone to slightly above atmospheric. This stream was then passed through a wet ice trap where the hydrogen was separated from the condensables in the stream leaving a mixture containing unreacted MEA and the products of the reaction.

The mixture of reacted MEA and products of the reaction were then analyzed for water by a Karl-Fisher procedure and for organics (amines) by capillary gas chromatography.

The conditions used in the examples and the results are set forth in the following table:

TABLE______________________________________ EXAMPLE NO.: 1 2 3 4______________________________________MEA conversion, % 17.49 29.11 37.32 46.47temperature, .degree.C. 150.6 157.4 162.9 168.2pressure, psig 615 615 615 615MEA SV, gmol/hr/kgcat 13.49 13.24 13.90 12.72H.sub.2, mole % 67.58 68.57 66.70 68.00EDA selectivity, % .9784 .9047 1.0048 .9033MeEDA selectivity, % .0950 .1251 .1548 .1840PIP selectivity, % 4.5295 5.5716 6.9662 8.9200EtEDA selectivity, % .0160 .0239 .0325 .0425DETA selectivity, % .8735 .9763 1.2908 1.1479AEEA selectivity, % 71.1099 59.9388 54.3441 41.6836AEP selectivity, % 3.3116 3.6457 3.7995 4.0922HEP selectivity, % 3.3916 5.3856 7.4799 10.0596TETA selectivity, % 15.6944 18.8765 17.1044 21.0448TEPA selectivity, % .0000 4.5517 7.8229 11.9222product EDA, mole % 2.0926 2.0257 2.2933 2.1711product MeEDA, mole % .1016 .1400 .1766 .2211product PIP, mole % 4.8437 6.2374 7.9494 10.7198product EtEDA, mole % .0171 .0268 .0371 .0511product DETA, mole % .9341 1.0930 1.4730 1.3795product AEEA, mole % 76.0432 67.1010 62.0139 50.0944product AEP, mole % 2.3609 2.7209 2.8905 3.2786product HEP, mole % 2.4179 4.0194 5.6904 8.0596product TETA, mole % 11.1888 14.0881 13.0123 16.8608product TEPA, mole % .0000 2.5478 4.4635 7.1639AEEA/PIP + AEP + 6.01 4.17 3.06 1.96HEP + DETA + EDA______________________________________

Claims

1. A continuously generated alkyleneamines producers composition comprising, based on 100% of the moles of the composition and exclusive of any MEA and water present,

a) about 50 to about 90 mole % AEEA,

b) less than about 3 mole % EDA but more than 0.01 mole % EDA,

c) less than about 2 mole % DETA but more than 0.01 mole % DETA,

d) about 5 to about 18 mole % of the combination of PIP, AEP and HEP,

e) about 5 to about 20 mole % of one or more of TETAs and TEPAs,

f) less than about 1 mole % of other polyalkylene polyamines,

g) a mole ratio of AEEA to the combination of PIP, AEP, HEP, DETA and EDA is greater than about 2.5,

h) an AEEA to EDA mole ratio greater than about 22 and

i) an AEEA to PIP mole ratio greater than about 7.

2. The composition of claim 1 wherein the amount of AEEA is about 60 to about 80 mole % of the composition.

3. The composition of claim 1 wherein the amount of AEEA is about 65 to about 80 mole % of the composition.

4. The composition of claim 1 wherein the combination of PIP, AEP and HEP is about 5 to about 15 mole % of the composition.

5. The composition of claim 1 wherein one or more of TETAs and TEPAs comprises about 5 to about 17 mole % of the composition.