Process for producing amines by reductive amination with recycle stream

Abstract

A process for producing amines by reductive amination, the process includes introducing a feed stream to a reaction zone, the feed stream comprising an amino alcohol and a reducing agent, introducing a recycle stream to a reaction zone, wherein the recycle stream comprises light alkylamines, and contacting the feed stream and the recycle stream with a catalyst in the reaction zone in the presence of hydrogen, and a product stream comprising ethyleneamines is produced. The catalyst includes a carrier component selected from alumina, silica, and combinations thereof; and an active component having a first metal, a second metal, and a third metal. The first metal is selected from cobalt, nickel, and copper, the second metal is selected from rhenium, ruthenium, chromium, zinc, sodium, calcium, magnesium, strontium, lithium, potassium, barium, cesium, lanthanum, tungsten, iron, silver, titanium, manganese, aluminum, rhodium, platinum, palladium, iridium, and combinations thereof, and the third metal is niobium.

Description

86261 -WO-PCT / DOW 86261 WO1PROCESS FOR PRODUCING AMINES BY REDUCTIVE AMINATION WITH RECYCLE STREAMCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 718,947 filed November 11, 2024, the entire disclosure of which is hereby incorporated by reference.TECHNICAL FIELD

[0002] Embodiments disclosed herein generally relate to chemical processing and, more specifically, to a catalyst and methods using the catalysts.BACKGROUND

[0003] Reductive amination is a chemical process that converts monoethanolamine (MEA) into ethyleneamines. Reductive amination of MEA may generate both desired and undesired ethyleneamine products. Examples of desired ethyleneamine products may include ethylenediamine (EDA), N-(2-aminoethyl)ethanolamine (AEEA), diethylenetriamine (DETA), piperazine (PIP), and / or N-(2-aminoethyl)piperazine (AEP), which are of high market value. Most of the EDA produced in industry is produced by continuous reaction of MEA and ammonia in the presence of hydrogen over a catalyst. During EDA production, light alkylamines, for example MA and EA, can be formed as by-products. The light alkylamines may then react with MEA or other amines to form unwanted by-products, which may include N- methylethylenediamine (NMEDA or methyl-EDA), and N-ethylethylenediamine (NEEDA or ethyl-EDA). Several plausible routes may result in NMEDA and NEEDA. NMEDA is often the dominant unwanted by-product. Separation of unwanted by-products that have a volatility similar to EDA is a present challenge. In many industries, NMEDA in EDA must be less than 1000 ppm in EDA. Conventional catalysts produce large amounts of NMEDA and NEEDA. An additional separation challenge includes several azeotropes formed, wherein azeotropes mixtures cannot be separated by conventional distillation. A present challenge in this chemical process is decreasing the formation of unwanted by-products and azeotropes.SUMMARY

[0004] A process for producing amines by reductive amination may comprise introducing a feed stream, the feed stream comprising an amino alcohol and a reducing agent, and hydrogen in a reaction zone of a reactor, contacting the feed stream with a catalyst in the reaction zone,86261 -WO-PCT / DOW 86261 WO2 and producing a product stream comprising ethyleneamines. Commonly MEA is contacted by a reductive amination catalyst and ammonia in the presence of hydrogen. A common molar ratio of ammonia to MEA is at least 2:1. The processes may be achieved by feeding the reactants to a tubular reaction zone. Conventional catalysts used in this process often results in unwanted by-products, which may include alkylamines. While producing EDA, conventional catalysts also produce light alkylamines (potentially by hydrogenolysis), such as methylamine (MA) and ethylamine (EA), that are often recycled with ammonia into the reactant feed. When MA and EA are recycled, they may further react with ethanolamines and ethyleneamines to produce several alkyl-ended ethyleneamines, which are undesired. As an example, methylamine and ethylamine can be formed by hydrogenolysis of MEA during the reductive amination of monoethanolamine with ammonia. The methylamine and ethylamine are capable of further reaction with ethanolamines or ethyleneamines to give several alkyl-ended ethyleneamines which are typically undesired. For example, recycled MA and EA can produce NMEDA and NEEDA respectively, from MEA or EDA, which are considered by-product impurities that are difficult to separate in downstream distillation steps. To meet industrial EDA specifications of less than 1000 ppm of NMEDA in EDA, high cost separation is required to remove NMEDA and NEEDA from the product stream due to the similarity in volatility to EDA. Additionally, the water produced in the reductive amination of MEA contributes to an amine / water azeotrope, which cannot be separated by conventional distillation. Both EDA and water and NMEDA and water form an azeotrope. There is a need for a catalyst that is capable of catalyzing the reductive amination of MEA with a reduced amount of unwanted by-products which can lead to difficulty to separate azeotropes. Specifically, smaller amounts of NMEDA and NEEDA, which could make difficult separations unnecessary, is needed. Conventional catalysts result in a high yield of unwanted by-products in which requires separation of difficult azeotropes. Though a wide variety of reductive amination catalysts are known in industry, the catalysts commonly used are hydrogenation catalysts. Nickel is a common catalyst component used in reductive amination, and may result in the relatively high content of the above-mentioned by-products. Conventional catalysts result in reaction performance where a variety of products are present in the process effluent stream, which necessitates separation of high market value products from low market value products and by-products. The composition of the product stream, and the degree of separation necessary to extract the desired product, may vary on a number of factors, which may include at least: catalyst composition, catalyst shape, reactant ratio, temperature, pressure, recycle stream composition, and reactant flow velocity. To reduce the amount of effort and cost86261 -WO-PCT / DOW 86261 WO3 spent on separation downstream, a catalyst capable of minimizing unwanted amine products, including NMEDA and NEEDA, under a variety of conditions is desired. More specifically, a catalyst which either minimizes the generation of MA and EA or minimizes the reaction of MA and EA with MEA or EDA to produce NMEDA and NEEDA, respectively, is desired. Embodiments disclosed and described herein, include catalysts comprising niobium that are suitable for reductive amination and reduce the generation of unwanted by-products.

[0005] According to one or more embodiments, a process for producing amines by reductive amination may comprise introducing a feed stream to a reaction zone, the feed stream comprising an amino alcohol and a reducing agent, introducing a recycle stream to a reaction zone, wherein the recycle stream comprises light alkylamines, contacting the feed stream and the recycle stream with a catalyst in the reaction zone in the presence of hydrogen, and producing a product stream comprising ethyleneamines, wherein the catalyst comprises a carrier component selected from the group consisting of alumina, silica, and combinations thereof, and an active component comprising a first metal, a second metal, and a third metal, wherein the first metal is selected from the group consisting of cobalt, nickel, and copper, the second metal is selected from a group consisting of rhenium, ruthenium, chromium, zinc, sodium, calcium, magnesium, strontium, lithium, potassium, barium, cesium, lanthanum, tungsten, iron, silver, titanium, manganese, aluminum, rhodium, platinum, palladium, iridium, and combinations thereof, and the third metal is niobium.

[0006] This summary is provided to introduce a selection of concepts that are further described in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0007] Additional features and advantages of the described embodiments will be set forth in the detailed description that follows. The additional features and advantages of the described embodiments will be, in part, readily apparent to those skilled in the art from that description or recognized by practicing the described embodiments, including the detailed description that follows as well as the claims.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1 is a bar graph of reactions 1 to 3 and 7 to 9, and compares the weight percentage generation of NMEDA resulting from contacting feed and simulated recycle streams with86261 -WO-PCT / DOW 86261 WO4Example Catalyst 1 and Comparative Example Catalyst A at a variety of MA concentrations in the ammonia feed.

[0009] FIG. 2 is a bar graph of reactions 4 to 6 and 10 to 12, and compares the weight percentage generation of NEED A resulting from contacting feed and simulated recycle streams with Example Catalyst 1 and Comparative Example Catalyst A at a variety of EA concentrations in the ammonia feed.DETAILED DESCRIPTION

[0010] Presently described, according to one or more embodiments, are catalysts for reductive amination, methods for producing catalysts, and methods for using catalysts. Catalysts described in this disclosure may comprise a carrier portion and an active catalyst portion.

[0011] As used in this disclosure, a “catalyst” refers to any substance that increases the rate of a specific chemical reaction. Catalysts described in this disclosure may be utilized to promote various reactions, such as, but not limited to, producing amines by reductive amination. Catalysts described in this disclosure may comprise a carrier component and an active component.

[0012] As used in this disclosure, an “effluent” generally refers to a stream that exits a system component such as a separation unit, a reactor, or reaction zone, following a separation or particular reaction, and generally has a different composition (at least proportionally) than the stream that entered the separation unit, reactor, or reaction zone.

[0013] As used in this disclosure, “product effluent” generally refers to a stream that exits a system component such as a reactor or reaction zone, following a particular reaction, and generally has a different composition (at least proportionally) than the stream that entered the reactor or reaction zone.

[0014] As used in this disclosure, “recycle stream” is a stream that includes MA, EA, and ammonia derived from a product effluent and is directed to and combined with the feed stream.

[0015] As used in this disclosure, “>N4” generally refers to a molecular structure comprising greater than or equal to four nitrogen atoms.

[0016] As used in this disclosure, “unwanted by-products” or “undesired by-products” generally refers to N-methylethylenediamine (NMEDA or methyl-EDA), N- ethylethylenediamine (NEEDA or ethyl-EDA), methylamine (MA), ethylamine (EA), and other alkylethyleneamines.86261 -WO-PCT / DOW 86261 WO5

[0017] As used throughout this disclosure, “carrier component” may be selected from the group consisting of alumina, silica, and combinations thereof. Examples include, but are not limited to, kieselguhrs, diatomaceous earths, and mixed silica-aluminas. Carrier components may be used as physical carriers for other components of the catalyst and, in embodiments, may have minimal chemical effect on the other components of the catalyst.

[0018] As used throughout this disclosure, “active component” may comprise one or more metals, one or more metal oxides, or combinations thereof.

[0019] As used in this disclosure, the “reaction zone” may be defined as a zone in the reactor containing the catalysts where the reaction is initiated.

[0020] As used in this disclosure, “calcining” or “calcine” may be defined as a treatment of a solid chemical compound whereby the compound is raised to a high temperature without fusing in order to drive off volatile matter or to effect changes such as oxidation and / or thermal decomposition. Calcining may be used to remove impurities or volatile substances.

[0021] As used in this disclosure, “alkylamines” may include, but are not limited to, methylamine (MA), ethylamine (EA), N-methylethylenediamine, N-ethylethylenediamine, N- methylated ethyleneamines, poly-N-methylated ethyleneamines, N-ethylated ethyleneamines, and poly-N-ethylated ethyleneamines.

[0022] As used in this disclosure, “light alkylamines” may refer to methylamine, ethylamine, and / or combinations thereof.

[0023] As used in this disclosure, “poly-N-alkylated ethylenediamine(s)” may be used to refer to bis(N-methyl-l,2-ethanediamine), bis (N-ethyl-l,2-ethanediamine, or N-methyl, N’ethyl- 1,2, -ethanediamine, and / or combinations thereof.

[0024] As used in this disclosure, “lighter amine(s)” or “light amine(s)” may be used to refer to one or more alkylamines. Examples of alkylamines includes methylamine (MA) and ethylamine (EA).

[0025] As used in this disclosure, “by-product impurities” or “by-products” or “impurities” may be referred to as unwanted products that may be difficult to separate in downstream distillation steps. These impurities may be made by various routes, including but not limited to, reaction of MEA with recycled light alkylamines.

[0026] As used in this disclosure, “space velocity” or “SV” (hr-1) may be defined as a ratio of mass flow rate (g / hr) of a feed stream to the mass of the catalyst (g) loaded in a reactor.86261 -WO-PCT / DOW 86261 WO6

[0027] As used in this disclosure, “selectivity” refers to a mass-based approximation rather than conventional molar based approximation. This distinction is used to compare results with mass-based production ratios calculated by technical centers and production personnel. As used in this disclosure, selectivity may be based on converted products, excluding unreacted feed material such as the reducing agent and the amino alcohol.

[0028] As used in this disclosure, “conversion” refers specifically to the conversion of MEA on a weight basis.

[0029] As used in this disclosure, “concentration of hydrogen” may be used to refer to the concentration of hydrogen with respect to MEA, the concentration of hydrogen with respect to ammonia, and / or the concentration of hydrogen with respect to the contents of total material in the reaction zone.

[0030] In embodiments of a process for producing amines by reductive amination, the process may comprise introducing a feed stream to a reaction zone, the feed stream comprising an amino alcohol and a reducing agent, introducing a recycle stream to a reaction zone, the recycle stream comprising light alkylamines contacting the feed stream and the recycle stream with a catalyst in the reaction zone in the presence of hydrogen, and producing a product stream comprising ethylenediamines, wherein the catalyst comprises a carrier component selected from the group consisting of alumina, silica, and combinations thereof, and an active component comprising a first metal, a second metal, and a third metal, wherein the first metal is selected from the group consisting of cobalt, nickel, and copper, the second metal selected from a group consisting of rhenium, ruthenium, chromium, zinc, sodium, calcium, magnesium, strontium, lithium, potassium, barium, cesium, lanthanum, tungsten, iron, silver, titanium, manganese, aluminum, rhodium, platinum, palladium, iridium, and combinations thereof, and the third metal is niobium.

[0031] In embodiments of a process for producing amines by reductive amination, the process comprises introducing a feed stream to a reaction zone, the feed stream comprising an amino alcohol and a reducing agent, introducing a recycle stream to a reaction zone, the recycle stream comprising light alkylamines and ammonia, and contacting the feed stream and the recycle stream with a catalyst in the reaction zone in the presence of hydrogen, producing a product stream comprising ethyleneamines, wherein the amino alcohol is monoethanolamine.

[0032] In embodiments of a process for producing amines by reductive amination, the process may comprise introducing a feed stream to a reaction zone, the feed stream comprising an amino86261 -WO-PCT / DOW 86261 WO7 alcohol and a reducing agent, introducing a recycle stream to a reaction zone, the recycle stream comprising light alkylamines, and contacting the feed stream and the recycle stream with a catalyst in the reaction zone in the presence of hydrogen, producing a product stream comprising ethyleneamines, wherein the reducing agent is ammonia.

[0033] In embodiments of a process for producing amines by reductive amination, the overall conversion of MEA may be from 20 wt. % to 99 wt. %. For example, the overall conversion of MEA may be from 20 wt. % to 90 wt. %, from 20 wt. % to 70 wt. %, from 20 wt. % to 50 wt. %, from 20 wt. % to 30 wt. %, from 30 wt. % to 99 wt. %, from 30 wt. % to 90 wt. %, from 30 wt. % to 70 wt. %, from 30 wt. % to 50 wt. %, from 50 wt. % to 99 wt. %, from 50 wt. % to 90 wt. %, from 50 wt. % to 70 wt. %, from 70 wt. % to 99 wt. %, from 70 wt. % to 90 wt. %, or from 90 wt. % to 99 wt. %

[0034] In embodiments of a process for producing amines by reductive amination, the molar ratio of reducing agent to amino alcohol may comprise from 1 :10 to 45:1, from 1 :10 to 40:1, from 1 :10 to 35:1, 1 :10 to 30:1, from 1 :10 to 25:1, from 1 :10 to 20:1, from 1 :10 to 15:1, from 1 :10 to 10:1, from 1 :10 to 5:1, from 1:10 to 1 :1, from 1 :10 to 1 :5, 1 :5 to 45:1, from 1 :5 to 40:1, from 1 :5 to 35:1, from 1 :5 to 30:1, from 1 :5 to 25:1, from 1 :5 to 20:1, from 1 :5 to 15:1, from 1 :5 to 10:1, from 1 :5 to 5:1, from 1 :5 to 1 :1, from 1:1 to 45:1, from 1 :1 to 40:1, from 1 :1 to 35:1, from 1 :1 to 30:1, from 1 :1 to 25:1, from 1 :1 to 20:1, from 1 :1 to 15:1, from 1 :1 to 10:1, from 1 :1 to 5:1, from 5:1 to 30:1, from 5:1 to 25:1, from 5:1 to 20:1, from 5:1 to 15:1, from 5:1 to 10:1, from 10:1 to 30:1, from 10:1 to 25:1, from 10:1 to 20:1, from 10:1 to 15:1, from 15:1 to 30:1, from 15:1 to 25:1, from 15:1 to 20:1, from 20:1 to 30:1, from 20:1 to 25:1, or from 25:1 to 30:1. If the molar ratio of the reducing agent to amino alcohol is too high, amino alcohol conversion may be too low and more energy may be required for the separation and recycle process of the reducing agent; however, if the molar ratio of the reducing agent to amino alcohol is too low, selectivity to desired ethyleneamines may decrease and numerous side reactions may occur.

[0035] In embodiments of a process for producing amines by reductive amination, the pressure in the reaction zone may be from 750 psi to 4000 psi, from 750 psi to 3500 psi, from 750 psi to 3000 psi, from 750 psi to 2500 psi, from 750 psi to 2000 psi, from 750 psi to 1500 psi, from 750 psi to 1000 psi, from 1000 psi to 4000 psi, from 1000 psi to 3500 psi, from 1000 psi to 3000 psi, from 1000 psi to 2500 psi, from 1000 psi to 2000 psi, from 1000 psi to 1500 psi, from 1500 psi to 4000 psi, from 1500 psi to 3500 psi from 1500 psi to 3000 psi, from 1500 psi to 2500 psi,86261 -WO-PCT / DOW 86261 WO8 from 1500 psi to 2000 psi, from 2000 psi to 4000 psi, from 2000 psi to 3500 psi, from 2000 psi to 3000 psi, or from 2500 psi to 3000 psi. If the pressure is too high, more energy consumption may be required; however, if the pressure is too low, the catalyst may lose activity and desired reactions may not occur.

[0036] In embodiments of a process for producing amines by reductive amination, the process may be conducted at a temperature that is from 120 °C to 300 °C. For instance, in embodiments the temperature may be from 120 °C to 275 °C, from 120 °C to 250 °C, from 120 °C to 225 °C, from 120 °C to 200 °C, from 120 °C to 175 °C, from 120 °C to 150 °C, from 150 °C to 300 °C, from 150 °C to 275 °C, from 150 °C to 250 °C, from 150 °C to 225 °C, from 150 °C to 200 °C, from 150 °C to 175 °C, from 175 °C to 300 °C, from 175 °C to 275 °C, from 175 °C to 250 °C, from 175 °C to 225 °C, from 175 °C to 200 °C, from 200 °C to 300 °C, from 200 °C to 275 °C, from 200 °C to 250 °C, from 200 °C to 225 °C, from 225 °C to 300 °C, , from 225 °C to 275 °C, from 225 °C to 250 °C, from 250 °C to 300 °C, from 250 °C to 275 °C, or from 275 °C to 300 °C. If the temperature is too high, this may result in higher energy consumption and significant side reactions may occur; however, if the temperature is too low, activity and conversion may be low.

[0037] In embodiments of a process for producing amines by reductive amination, the feed stream may further comprise water, and the mass of water may be less than or equal to 30 wt. % of the mass of amino alcohol in the feed stream. For instance, in embodiments the mass of water may be less than or equal to 25 wt. %, 20 wt. %, 15 wt. %, or less than or equal to 10 wt. % of the mass of amino alcohol in the feed stream. If the mass of the water is too high catalyst stability and production rate may be reduced, and more wastewater may be generated.

[0038] In embodiments of a process for producing amines by reductive amination, hydrogen may be supplied to the reaction zone as a separate stream from the amino alcohol and the reducing agent. In embodiments of a process for producing amines by reductive amination, hydrogen may be supplied to the reaction zone as a component of the feed stream, which also includes the amino alcohol and the reducing agent. In one or more embodiments of a process for producing amines by reductive amination, hydrogen may be supplied to the reaction zone as a component of the recycle stream.

[0039] In embodiments of a process for producing amines by reductive amination, the MA concentration in the recycle stream may be from 4500 ppm to 20500 ppm based on ammonia concentration in the recycle stream. For instance, the MA concentration in the recycle stream86261 -WO-PCT / DOW 86261 WO9 may be from 4500 ppm to 18000 ppm, from 4500 ppm to 16000 ppm, from 4500 ppm to 14000 ppm, from 4500 ppm to 12000 ppm, from 4500 ppm to 10000 ppm, from 4500 ppm to 8000 ppm, from 4500 ppm to 6000 ppm, from 6000 ppm to 18000 ppm, from 6000 ppm to 16000 ppm, from 6000 ppm to 14000 ppm, from 6000 ppm to 12000 ppm, from 6000 ppm to 10000, from 6000 ppm to 8000 ppm, from 8000 ppm to 18000 ppm, from 8000 ppm to 16000 ppm, from 8000 ppm to 14000 ppm, from 8000 ppm to 12000 ppm, from 8000 ppm to 10000 ppm, from 10000 ppm to 18000 ppm, from 10000 ppm to 16000 ppm, from 10000 ppm to 14000 ppm, from 10000 ppm to 12000 ppm, from 12000 ppm to 18000 ppm, from 12000 ppm to 16000 ppm, from 12000 ppm to 14000 ppm, from 14000 ppm to 18000 ppm, from 14000 ppm to 16000 ppm, or from 16000 ppm to 18000 ppm MA in the recycle stream based on ammonia concentration in the recycle stream.

[0040] In embodiments of a process for producing amines by reductive amination, the EA concentration in the recycle stream may be from 4500 ppm to 13000 ppm based on ammonia concentration in the recycle stream. For instance, the EA concentration in the recycle stream may be from 4500 ppm to 13000 ppm, from 4500 ppm to 11000 ppm, from 4500 ppm to 9000 ppm, from 4500 ppm to 7000 ppm, from 4500 ppm to 5000, from 5000 ppm to 13000 ppm, from 5000 ppm to 11000 ppm, from 5000 ppm to 9000 ppm, from 5000 ppm to 7000 ppm, from 7000 ppm to 13000 ppm, from 7000 ppm to 11000 ppm, from 7000 ppm to 9000 ppm, from 9000 ppm to 13000 ppm, from 9000 ppm to 11000 ppm, or from 11000 ppm to 13000 ppm EA in the recycle stream based on ammonia concentration in the recycle stream.

[0041] In embodiments of a process for producing amines by reductive amination the hydrogen concentration in the reaction zone may be from 0.0001 mol.% to 50 mol.%. For instance, in embodiments the concentration of hydrogen in the reaction zone relative to the total quantity of H2, MEA, and NH3 may be from 0.0001 mol.% to 45 mol.%, from 0.0001 mol.% to 40 mol.%, from 0.0001 mol.% to 35 mol.%, from 0.0001 mol.% to 30 mol.%, from 0.0001 mol.% to 25 mol.%, from 0.0001 mol.% to 20 mol.%, from 0.0001 mol.% to 15 mol.%, from 0.0001 mol.% to 10 mol.%, from 0.0001 mol.% to 5 mol.%, from 5 mol.% to 50 mol.%, from 5 mol.% to 45 mol.%, from 5 mol.% to 30 mol.%, from 5 mol.% to 35 mol.%, from 5 mol.% to 25 mol.%, from 5 mol.% to 20 mol.%, from 5 mol.% to 15 mol.%, from 5 mol.% to 10 mol.%, from 10 mol.% to 50 mol.%, from 10 mol.% to 45 mol.%, from 10 mol.% to 40 mol.%, from 10 mol.% to 35 mol.%, from 10 mol.% to 30 mol.%, from 10 mol.% to 25 mol.%, from 10 mol.% to 20 mol.%, from 10 mol.% to 15 mol.%, from 15 mol.% to 50 mol.%, from 15 mol.% to 45 mol.%, from 1586261 -WO-PCT / DOW 86261 WO10 mol.% to 40 mol.%, from 15 mol.% to 35 mol.%, from 15 mol.% to 30 mol.%, from 15 mol.% to 25 mol.%, from 15 mol.% to 20 mol.%, from 20 mol.% to 50 mol.%, from 20 mol.% to 45 mol.%, from 20 mol.% to 40 mol.%, from 20 mol.% to 35 mol.%, from 20 mol.% to 30 mol.%, from 20 mol.% to 25 mol.%, from 25 mol.% to 50 mol.%, from 25 mol.% to 45 mol.%, from 25 mol.% to 40 mol.%, from 25 mol.% to 35 mol.%, from 25 mol.% to 30 mol.%, from 30 mol.% to 50 mol.%, from 30 mol.% to 45 mol.%, from 30 mol.% to 40 mol.%, from 30 mol.% to 35 mol.%, from 35 mol.% to 50 mol.%, from 35 mol.% to 45 mol.%, from 35 mol.% to 40 mol.%, from 40 mol.% to 50 mol.%, from 40 mol.% to 45 mol.%, or from 45 mol.% to 50 mol.%. If too much hydrogen is present in the reaction zone, selectivity may be decreased. Additionally, if too little hydrogen is present in the reaction zone the catalyst may deactivate or lose activity.

[0042] In embodiments of a process for producing amines by reductive amination, the feed stream may be fed into the reaction zone at a space velocity (SV) from 0.5 hr'1to 13 hr'1. For instance, in embodiments the space velocity of the feed stream may be from 0.5 hr'1to 12 hr'1, from 0.5 hr'1to 11 hr'1, from 0.5 hr'1to 10 hr'1, from 0.5 hr'1to 9 hr'1, from 0.5 hr'1to 8 hr'1, from 0.5 hr'1to 7 hr'1, from 0.5 hr'1to 6 hr'1, from 0.5 hr'1to 5 hr'1, from 0.5 hr'1to 4 hr'1, from 0.5 hr'1to 3 hr'1, from 0.5 hr'1to 2 hr'1, from 0.5 hr'1to 1 hr'1, from 1 hr'1to 13 hr'1, from 1 hr'1to 12 hr'1, from 1 hr'1to 11 hr'1, from 1 hr'1to 10 hr'1, from 1 hr'1to 9 hr'1, from 1 hr'1to 8 hr'1, from 1 hr'1to 7 hr'1, from 1 hr'1to 6 hr'1, from 1 hr'1to 5 hr'1, from 1 hr'1to 4 hr'1, from 1 hr'1to 3 hr'1, from 1 hr'1to 2 hr'1, from 2 hr'1to 13 hr'1, from 2 hr'1to 12 hr'1, from 2 hr'1to 11 hr'1, from 2 hr'1to 10 hr'1, from 2 hr'1to 9 hr'1, from 2 hr'1to 8 hr'1, from 2 hr'1to 7 hr'1, from 2 hr'1to 6 hr'1, from 2 hr'1to 5 hr'1, from 2 hr'1to 4 hr'1, from 2 hr'1to 3 hr'1, from 3 hr'1to 13 hr'1, from 3 hr'1to 12 hr'1, from 3 hr'1to 11 hr'1, from 3 hr'1to 10 hr'1, from 3 hr'1to 9 hr'1, from 3 hr'1to 8 hr'1, from 3 hr'1to 7 hr'1, from 3 hr'1to 6 hr'1, from 3 hr'1to 5 hr'1, from 3 hr'1to 4 hr'1, from 5 hr'1to 13 hr'1, from 5 hr'1to 12 hr'1, from 5 hr'1to 11 hr'1, from 5 hr'1to 10 hr'1, from 5 hr'1to 9 hr'1, from 5 hr'1to 8 hr'1, from 5 hr'1to 7 hr'1, from 5 hr'1to 6 hr'1, from 10 hr'1to 13 hr'1, from 10 hr'1to 12 hr'1, from 10 hr'1to 11 hr'1, from 11 hr'1to 13 hr'1, from 11 hr'1to 12 hr'1, or from 12 hr'1to 13 hr'1. If the space velocity of the feed stream is too high, the conversion will be low; however, if the space velocity of the feed stream is too low, selectivity of EDA may be reduced.

[0043] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed86261 -WO-PCT / DOW 86261 WO11 stream, to a catalyst in which one or more of the active components is impregnated into the carrier component.

[0044] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst in which the carrier component is alumina. In another embodiment the carrier component is silica. In yet another embodiment, the carrier component may comprise a mixture of alumina and silica.

[0045] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst having a carrier component comprising from 65 wt. % to 95 wt. % alumina, based on the total weight of the carrier component. For instance, in embodiments the carrier component may comprise from 65 wt. % to 90 wt. %, from 65 wt. % to 85 wt. %, from 65 wt. % to 80 wt. %, from 65 wt. % to 75 wt. %, from 65 wt. % to 70 wt. %, from 70 wt. % to 90 wt. %, from 70 wt. % to 85 wt. %, from 70 wt. % to 80 wt. %, from 70 wt. % to 75 wt. %, from 75 wt. % to 90 wt. %, from 75 wt. % to 85 wt. %, from 75 wt. % to 80 wt. %, from 80 wt. % to 90 wt. %, from 80 wt. % to 85 wt. %, from 85 wt. % to 90 wt. %, or from 90 wt. % to 95 wt. % alumina. If the amount of alumina is too high, the selectivity of EDA may decrease over time and the selectivity for AEEA may increase over time; however, if the amount of alumina is too low a loss of catalyst activity or selectivity may occur.

[0046] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst having a carrier component that comprises from 5 wt. % to 35 wt. % silica, based on the total weight of the carrier component. For instance, in embodiments the carrier component may comprise from 5 wt. % to 35 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 10 wt. %, from 10 wt. % to 35 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 25 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 15 wt. %, from 15 wt. % to 35 wt. %, from 15 wt. % to 30 wt. %, from 15 wt. % to 25 wt. %, from 15 wt. % to 20 wt. %, from 20 wt. % to 35 wt. %, from 20 wt. % to 30 wt. %, from 20 wt. % to 25 wt. %, from 25 wt. % to 35 wt. %, from 25 wt. % to 30 wt. %, or from 30 wt. % to 35 wt. % silica. If the amount of silica is too high the total metals to be impregnated onto the carrier may be affected and may result in loss of catalyst activity or86261 -WO-PCT / DOW 86261 WO12 selectivity; however, if the amount of silica is too low, the selectivity of EDA may decrease over time and the selectivity for AEEA may increase over time.

[0047] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst in which one of the first metal or the second metal may be nickel and the other of the first metal or the second metal may be rhenium. The third metal may be niobium.

[0048] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst comprising an active component comprising a first metal, a second metal, and a third metal, wherein the first metal is selected from the group consisting of cobalt, nickel, and copper, the second metal is selected from a group consisting of rhenium, ruthenium, chromium, zinc, sodium, calcium, magnesium, strontium, lithium, potassium, barium, cesium, lanthanum, tungsten, iron, silver, titanium, manganese, aluminum, rhodium, platinum, palladium, iridium, and combinations thereof, and the third metal is niobium, in which the ratio of the first metal to the second metal (based on the weight percent of each metal element to the total catalyst) may be from 1 :1 to 10:1. For instance, in embodiments the ratio may be from 1 :1 to 9:1, from 1 :1 to 8:1, from 1 :1 to 7:1, from 1 :1 to 6:1, from 1 :1 to 5:1, from 1 :1 to 4, from 1 :1 to 3:1, from 1 :1 to 2:1, from 2:1 to 10:1, from 2:1 to 9:1, from 2:1 to 8:1, from 2:1 to 7:1, from 2:1 to 6:1, from 2:1 to 5:1, from 2:1 to 4:1, from 2:1 to 3:1, from 3:1 to 10:1, from 3:1 to 9:1, from 3:1 to 8:1, from 3:1 to 7:1, from 3:1 to 6:1, from 3:1 to 5, from 3:1 to 4:1, from 4:1 to 10:1, from 4:1 to 9:1, from 4:1 to 8:1, from 4:1 to 7:1, from 4:1 to 6:1, from 4:1 to 5:1, from 5:1 to 10:1, from 5:1 to 9:1, from 5:1 to 8:1, from 5:1 to 7:1, from 5:1 to 6:1, from 6:1 to 10:1, from 6:1 to 9:1, from 6:1 to 8:1, from 6:1 to 7:1, from 7:1 to 10:1, from 7:1 to 9:1, from 7:1 to 8:1, from 8:1 to 10:1, from 8:1 to 9:1, or from 9:1 to 10:1. If the ratio of nickel to rhenium is too high, activity and / or desired selectivity may be lowered; however, if the ratio of nickel to rhenium is too low, activity and / or desired selectivity may be lowered. In embodiments, the first metal may be nickel and the second metal may be rhenium.

[0049] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst comprising an active component comprising a first metal, a second metal, and a third metal, wherein the first metal is selected from the group consisting of cobalt, nickel, and copper, the second metal is selected from a group consisting of rhenium, ruthenium,86261 -WO-PCT / DOW 86261 WO13 chromium, zinc, sodium, calcium, magnesium, strontium, lithium, potassium, barium, cesium, lanthanum, tungsten, iron, silver, titanium, manganese, aluminum, rhodium, platinum, palladium, iridium, and combinations thereof, and the third metal is niobium, in which the ratio of the first metal to the second metal, wherein the ratio is an atomic ratio of the metal elements, may be from 1 :1 to 50:1. For instance, in embodiments the ratio may be from 1 :1 to 49:1, from 1 :1 to 48:1, from 1 :1 to 47:1, from 1 :1 to 46:1, from 1 :1 to 45:1, from 1 :1 to 44:1, from 1 :1 to 43:1, from 1 :1 to 42:1, from 1 :1 to 41:1, from 1 :1 to 40:1, from 1 :1 to 39:1, from 1 :1 to 38:1, from 1 :1 to 37:1, from 1 :1 to 36:1, from 1 :1 to 35:1, from 1 :1 to 34:1, from 1 :1 to 33:1, from1 :1 to 32:1, from 1 :1 to 31 :1, from 1 :1 to 30:1, from 1 :1 to 29:1, from 1 :1 to 28:1, from 1 :1 to 27:1, from 1 :1 to 26:1, from 1 :1 to 25:1, from 1 :1 to 24:1, from 1 :1 to 23:1, from 1 :1 to 22:1, from 1 :1 to 21 :1, from 1 :1 to 20:1, from 1 :1 to 19:1, from 1 :1 to 18:1, from 1 :1 to 17:1, from1 :1 to 16:1, from 1 :1 to 15:1, from 1 :1 to 14:1, from 1 :1 to 13:1, from 1 :1 to 12:1, from 1 :1 to 11 :1, from 1 :1 to 10:1, from 1 :1 to 9:1, from 1 :1 to 8:1, from 1 :1 to 7:1, from 1 :1 to 6:1, from 1 :1 to 5:1, from 1 :1 to 4:1, from 1 :1 to 3:1, from 1:1 to 2:1, from 1 :1 to 5:1, from 1 :1 to 4:1, from 1 :1 to 3:1, from 1 :1 to 2:1, from 2:1 to 50:1, from 2:1 to 49:1, from 2:1 to 48:1, from 2:1 to 47:1, from 2:1 to 46:1, from 2:1 to 45:1, from 2:1 to 44:1, from 2:1 to 43:1, from 2:1 to 42:1, from 2:1 to 41 :1, from 2:1 to 40:1, from 2:1 to 39:1, from 2:1 to 38:1, from 2:1 to 37:1, from2:1 to 36:1, from 2:1 to 35:1, from 2:1 to 34:1, from 2:1 to 33:1, from 2:1 to 32:1, from 2:1 to32:1, from 2:1 to 30:1, from 2:1 to 29:1, from 2:1 to 28:1, from 2:1 to 27:1, from 2:1 to 26:1, from 2:1 to 25:1, from 2:1 to 24:1, from 2:1 to 23:1, from 2:1 to 22:1, from 2:1 to 21 :1, from2:1 to 20:1, from 2:1 to 19:1, from 2:1 to 18:1, from 2:1 to 17:1, from 2:1 to 16:1, from 2:1 to 15:1, from 2:1 to 14:1, from 2:1 to 13:1, from 2:1 to 12:1, from 2:1 to 11 :1, from 2:1 to 10:1, from 2:1 to 5:1, from 2:1 to 4:1, from 2:1 to 3:1, from 3:1 to 50:1, from 3:1 to 47:1, from 3:1 to46:1, from 3:1 to 45:1, from 3:1 to 44:1, from 3:1 to 43:1, from 3:1 to 42:1, from 3:1 to 41 :1, from 3:1 to 40:1, from 3:1 to 39:1, from 3:1 to 38:1, from 3:1 to 37:1, from 3:1 to 36:1, from3:1 to 35:1, from 3:1 to 34:1, from 3:1 to 33:1, from 3:1 to 32:1, from 3:1 to 20:1, from 3:1 to 10:1, from 3:1 to 5:1, from 3:1 to 4:1, from 4:1 to 48:1, from 4:1 to 47:1, from 4:1 to 46:1, from 4:1 to 45:1, from 4:1 to 44:1, from 4:1 to 43:1, from 4:1 to 42:1, from 4:1 to 41 :1, from 4:1 to 40:1, from 4:1 to 39:1, from 4:1 to 38:1, from 4:1 to 37:1, from 4:1 to 36:1, from 4:1 to 35:1, from 4:1 to 34:1, from 4:1 to 33:1, from 4:1 to 32:1, from 4:1 to 20:1, from 4:1 to 10:1, from4:1 to 5:1, from 5:1 to 50:1, from 5:1 to 46:1, from 5:1 to 45:1, from 5:1 to 44:1, from 5:1 to 43:1, from 5:1 to 42:1, from 5:1 to 41:1, from 5:1 to 40:1, from 5:1 to 39:1, from 5:1 to 38:1, from 5:1 to 37:1, from 5:1 to 36:1, from 5:1 to 35:1, from 5:1 to 34:1, from 5:1 to 33:1, from86261 -WO-PCT / DOW 86261 WO145:1 to 32:1, from 5:1 to 20:1, from 5:1 to 10:1, from 10:1 to 50:1, from 10:1 to 47:1, from 10:1 to 46:1, from 10:1 to 45:1, from 10:1 to 44:1, from 10:1 to 43:1, from 10:1 to 42:1, from 10:1 to 41 :1, from 10:1 to 40:1, from 10:1 to 39:1, from 10:1 to 38:1, from 10:1 to 37:1, from 10:1 to 36:1, from 10:1 to 35:1, from 10:1 to 34:1, from 10:1 to 33:1, from 10:1 to 32:1, from 10:1 to 20:1, from 10:1 to 14:1, from 10:1 to 13:1, from 10:1 to 12:1, from 10:1 to 11 :1, from 11 :1 to 14:1, from 11 :1 to 13:1, from 11 :1 to 12:1, from 12:1 to 14:1, from 12:1 to 13:1, from 13:1 to 14:1, from 20:1 to 50:1, from 20:1 to 47:1, from 20:1 to 46:1, from 20:1 to 45:1, from 20:1 to 44:1, from 20:1 to 43:1, from 20:1 to 42:1, from 20:1 to 41 :1, from 20:1 to 40:1, from 20:1 to 39:1, from 20:1 to 38:1, from 20:1 to 37:1, from 20:1 to 36:1, from 20:1 to 35:1, from 20:1 to 34:1, from 20:1 to 33:1, from 20:1 to 30:1, from 30:1 to 50:1, from 30:1 to 47:1, from 30:1 to 46:1, from 30:1 to 45:1, from 30:1 to 44:1, from 30:1 to 43:1, from 30:1 to 42:1, from 30:1 to 41 :1, from 30:1 to 40:1, from 30:1 to 39:1, from 30:1 to 38:1, from 30:1 to 37:1, from 30:1 to 36:1, from 30:1 to 35:1, from 30:1 to 34:1, from 30:1 to 33:1, from 40:1 to 49:1, from 40:1 to 48:1, from 40:1 to 47:1, from 40:1 to 46:1, from 40:1 to 45:1, from 40:1 to 44:1, from 40:1 to 43:1, from 40:1 to 42:1, from 40:1 to 41 :1, from 45:1 to 50:1, from 45:1 to 49:1, from 45:1 to 48:1, from 45:1 to 47:1, from 45:1 to 46:1, or from 46:1 to 50:1. As used herein, the above ratio is a ratio of metal atoms and does not include non-metal components of compounds such as, for example, oxides or salts. If the ratio of nickel to rhenium is too high, activity and / or desired selectivity may be lowered; however, if the ratio of nickel to rhenium is too low, activity and / or desired selectivity may be lowered. In embodiments, the first metal may be nickel and the second metal may be rhenium.

[0050] In embodiments a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst comprising an active component comprising a first metal, a second metal, and a third metal, wherein the first metal is selected from the group consisting of cobalt, nickel, and copper, the second metal is selected from a group consisting of rhenium, ruthenium, chromium, zinc, sodium, calcium, magnesium, strontium, lithium, potassium, barium, cesium, lanthanum, tungsten, iron, silver, titanium, manganese, aluminum, rhodium, platinum, palladium, iridium, and combinations thereof, and the third metal is niobium, in which the ratio of the first metal to the third metal, wherein the ratio is an atomic ratio of the metal elements, may be from 1 :1 to 50:1. For instance, in embodiments the ratio may be from 1 :1 to 49:1, from 1 :1 to 48:1, from 1 :1 to 47:1, from 1 :1 to 46:1, from 1 :1 to 45:1, from 1 :1 to 44:1, from 1 :1 to 43:1, from 1 :1 to 42:1, from 1 :1 to 41:1, from 1 :1 to 40:1, from 1 :1 to 39:1, from 1 :1 to 38:1,86261 -WO-PCT / DOW 86261 WO15 from 1 :1 to 37:1, from 1 :1 to 36:1, from 1 :1 to 35:1, from 1 :1 to 34:1, from 1 :1 to 33:1, from1 :1 to 32:1, from 1 :1 to 31 :1, from 1 :1 to 30:1, from 1 :1 to 29:1, from 1 :1 to 28:1, from 1 :1 to27:1, from 1 :1 to 26:1, from 1 :1 to 25:1, from 1 :1 to 24:1, from 1 :1 to 23:1, from 1 :1 to 22:1, from 1 :1 to 21 :1, from 1 :1 to 20:1, from 1 :1 to 19:1, from 1 :1 to 18:1, from 1 :1 to 17:1, from1 :1 to 16:1, from 1 :1 to 15:1, from 1 :1 to 14:1, from 1 :1 to 13:1, from 1 :1 to 12:1, from 1 :1 to 11 :1, from 1 :1 to 10:1, from 1 :1 to 9:1, from 1 :1 to 8:1, from 1 :1 to 7:1, from 1 :1 to 6:1, from 1 :1 to 5:1, from 1 :1 to 4:1, from 1 :1 to 3:1, from 1:1 to 2:1, from 1 :1 to 5:1, from 1 :1 to 4:1, from 1 :1 to 3:1, from 1 :1 to 2:1, from 2:1 to 50:1, from 2:1 to 49:1, from 2:1 to 48:1, from 2:1 to 47:1, from 2:1 to 46:1, from 2:1 to 45:1, from 2:1 to 44:1, from 2:1 to 43:1, from 2:1 to 42:1, from 2:1 to 41 :1, from 2:1 to 40:1, from 2:1 to 39:1, from 2:1 to 38:1, from 2:1 to 37:1, from2:1 to 36:1, from 2:1 to 35:1, from 2:1 to 34:1, from 2:1 to 33:1, from 2:1 to 32:1, from 2:1 to32:1, from 2:1 to 30:1, from 2:1 to 29:1, from 2:1 to 28:1, from 2:1 to 27:1, from 2:1 to 26:1, from 2:1 to 25:1, from 2:1 to 24:1, from 2:1 to 23:1, from 2:1 to 22:1, from 2:1 to 21 :1, from2:1 to 20:1, from 2:1 to 19:1, from 2:1 to 18:1, from 2:1 to 17:1, from 2:1 to 16:1, from 2:1 to 15:1, from 2:1 to 14:1, from 2:1 to 13:1, from 2:1 to 12:1, from 2:1 to 11 :1, from 2:1 to 10:1, from 2:1 to 5:1, from 2:1 to 4:1, from 2:1 to 3:1, from 3:1 to 50:1, from 3:1 to 47:1, from 3:1 to46:1, from 3:1 to 45:1, from 3:1 to 44:1, from 3:1 to 43:1, from 3:1 to 42:1, from 3:1 to 41 :1, from 3:1 to 40:1, from 3:1 to 39:1, from 3:1 to 38:1, from 3:1 to 37:1, from 3:1 to 36:1, from3:1 to 35:1, from 3:1 to 34:1, from 3:1 to 33:1, from 3:1 to 32:1, from 3:1 to 20:1, from 3:1 to 10:1, from 3:1 to 5:1, from 3:1 to 4:1, from 4:1 to 48:1, from 4:1 to 47:1, from 4:1 to 46:1, from 4:1 to 45:1, from 4:1 to 44:1, from 4:1 to 43:1, from 4:1 to 42:1, from 4:1 to 41 :1, from 4:1 to 40:1, from 4:1 to 39:1, from 4:1 to 38:1, from 4:1 to 37:1, from 4:1 to 36:1, from 4:1 to 35:1, from 4:1 to 34:1, from 4:1 to 33:1, from 4:1 to 32:1, from 4:1 to 20:1, from 4:1 to 10:1, from4:1 to 5:1, from 5:1 to 50:1, from 5:1 to 46:1, from 5:1 to 45:1, from 5:1 to 44:1, from 5:1 to 43:1, from 5:1 to 42:1, from 5:1 to 41:1, from 5:1 to 40:1, from 5:1 to 39:1, from 5:1 to 38:1, from 5:1 to 37:1, from 5:1 to 36:1, from 5:1 to 35:1, from 5:1 to 34:1, from 5:1 to 33:1, from5:1 to 32:1, from 5:1 to 20:1, from 5:1 to 10:1, from 10:1 to 50:1, from 10:1 to 47:1, from 10:1 to 46:1, from 10:1 to 45:1, from 10:1 to 44:1, from 10:1 to 43:1, from 10:1 to 42:1, from 10:1 to 41 :1, from 10:1 to 40:1, from 10:1 to 39:1, from 10:1 to 38:1, from 10:1 to 37:1, from 10:1 to 36:1, from 10:1 to 35:1, from 10:1 to 34:1, from 10:1 to 33:1, from 10:1 to 32:1, from 10:1 to 20:1, from 10:1 to 15:1, from 10:1 to 14:1, from 10:1 to 13:1, from 10:1 to 12:1, from 10:1 to 11 :1, from 11 :1 to 15:1, from 11 :1 to 14:1, from 11 :1 to 13:1, from 11 :1 to 12:1, from 12:1 to 15:1, from 12:1 to 14:1, from 12:1 to 13:1, from 13:1 to 15:1, from 13:1 to 14:1, from 14:186261 -WO-PCT / DOW 86261 WO16 to 15:1, from 20:1 to 50:1, from 20:1 to 47:1, from 20:1 to 46:1, from 20:1 to 45:1, from 20:1 to 44:1, from 20:1 to 43:1, from 20:1 to 42:1, from 20:1 to 41 :1, from 20:1 to 40:1, from 20:1 to 39:1, from 20:1 to 38:1, from 20:1 to 37:1, from 20:1 to 36:1, from 20:1 to 35:1, from 20:1 to 34:1, from 20:1 to 33:1, from 20:1 to 30:1, from 30:1 to 50:1, from 30:1 to 47:1, from 30:1 to 46:1, from 30:1 to 45:1, from 30:1 to 44:1, from 30:1 to 43:1, from 30:1 to 42:1, from 30:1 to 41 :1, from 30:1 to 40:1, from 30:1 to 39:1, from 30:1 to 38:1, from 30:1 to 37:1, from 30:1 to 36:1, from 30:1 to 35:1, from 30:1 to 34:1, from 30:1 to 33:1, from 40:1 to 49:1, from 40:1 to 48:1, from 40:1 to 47:1, from 40:1 to 46:1, from 40:1 to 45:1, from 40:1 to 44:1, from 40:1 to 43:1, from 40:1 to 42:1, from 40:1 to 41 :1, from 45:1 to 50:1, from 45:1 to 49:1, from 45:1 to 48:1, from 45:1 to 47:1, from 45:1 to 46:1, or from 46:1 to 50:1. As used herein, the above ratio is a ratio of metal atoms and does not include non-metal components of compounds such as, for example, oxides or salts. If the ratio of nickel to niobium is too high, dispersion may be poor, reducing activity and selectivity; however, if the ratio of nickel to niobium is too low, dispersion may be poor, reducing activity and selectivity. In embodiments, the first metal may be nickel.

[0051] In embodiments, a catalyst for producing amines by reductive amination comprises an atomic ratio of the second metal to the third metal, wherein the ratio is an atomic ratio of the metal elements, that is from 0.5:1 to 10:1. For example, in embodiments the ratio may be from 0.5:1 to 10 :1, from 0.5:1 to 9.6:1, from 0.5:1 to 9.2:1, from 0.5:1 to 8.9:1, from 0.5:1 to 8.5:1, from 0.5:1 to 8.1 :1, from 0.5:1 to 7.7:1, from 0.5:1 to 7.3:1, from 0.5:1 to 7:1, from 0.5:1 to 6.6:1, from 0.5:1 to 6.2:1, from 0.5:1 to 5.8:1, from 0.5:1 to 5.4:1, from 0.5:1 to 5.1 :1, from 0.5:1 to 4.7:1, from 0.5:1 to 4.3:1, from 0.5:1 to 3.9:1, from 0.5:1 to 3.5:1, from 0.5:1 to 3.2:1, from 0.5:1 to 2.8:1, from 0.5:1 to 2.4:1, from 0.5:1 to 2:1, from 0.5:1 to 1.6:1, from 0.5:1 to 1.3:1, from 0.9:1 to 10:1, from 0.9:1 to 9.6:1, from 0.9:1 to 9.2:1, from 0.9:1 to 8.9:1, from 0.9:1 to 8.5:1, from 0.9:1 to 8.1 :1, from 0.9:1 to 7.7:1, from 0.9:1 to 7.3:1, from 0.9:1 to 7:1, from 0.9:1 to 6.6:1, from 0.9:1 to 6.2:1, from 0.9:1 to 5.8:1, from 0.9:1 to 5.4:1, from 0.9:1 to 5.1 :1, from 0.9:1 to 4.7:1, from 0.9:1 to 4.3:1, from 0.9:1 to 3.9:1, from 0.9:1 to 3.5:1, from 0.9:1 to 3.2:1, from 0.9:1 to 2.8:1, from 0.9:1 to 2.4:1, from 0.9:1 to 2:1, from 0.9:1 to 1.6:1, from 1.3:1 to 10:1, from 1.3:1 to 9.6:1, from 1.3:1 to 9.2:1, from 1.3:1 to 8.9:1, from 1.3:1 to 8.5:1, from 1.3:1 to 8.1 :1, from 1.3:1 to 7.7:1, from 1.3:1 to 7.3:1, from 1.3:1 to 7:1, from 1.3:1 to 6.6:1, from 1.3:1 to 6.2:1, from 1.3:1 to 5.8:1, from 1.3:1 to 5.4:1, from 1.3:1 to 5.1 :1, from 1.3:1 to 4.7:1, from 1.3:1 to 4.3:1, from 1.3:1 to 3.9:1, from 1.3:1 to 3.5:1, from 1.3:1 to 3.2:1, from 1.3:1 to 2.8:1, from 1.3:1 to 2.4:1, from 1.3:1 to 2:1, from 1.6:1 to 10:1, from 1.6:1 to 9.6:1,86261 -WO-PCT / DOW 86261 WO17 from 1.6:1 to 9.2:1, from 1.6:1 to 8.9:1, from 1.6:1 to 8.5:1, from 1.6:1 to 8.1 :1, from 1.6:1 to 7.7:1, from 1.6:1 to 7.3:1, from 1.6:1 to 7:1, from 1.6:1 to 6.6:1, from 1.6:1 to 6.2:1, from 1.6:1 to 5.8:1, from 1.6:1 to 5.4:1, from 1.6:1 to 5.1 :1, from 1.6:1 to 4.7:1, from 1.6:1 to 4.3:1, from 1.6:1 to 3.9:1, from 1.6:1 to 3.5:1, from 1.6:1 to 3.2:1, from 1.6:1 to 2.8:1, from 1.6:1 to 2.4:1, from 2:1 to 10:1, from 2:1 to 9.6:1, from 2:1 to 9.2:1, from 2:1 to 8.9:1, from 2:1 to 8.5:1, from 2:1 to 8.1 :1, from 2:1 to 7.7:1, from 2:1 to 7.3:1, from 2:1 to 7:1, from 2:1 to 6.6:1, from 2:1 to 6.2:1, from 2:1 to 5.8:1, from 2:1 to 5.4:1, from 2:1 to 5.1 :1, from 2:1 to 4.7:1, from 2:1 to 4.3:1, from 2:1 to 3.9:1, from 2:1 to 3.5:1, from 2:1 to 3.2:1, from 2:1 to 2.8:1, from 2.4:1 to 10:1, from 2.4:1 to 9.6:1, from 2.4:1 to 9.2:1, from 2.4:1 to 8.9:1, from 2.4:1 to 8.5:1, from 2.4:1 to 8.1 :1, from 2.4:1 to 7.7:1, from 2.4:1 to 7.3:1, from 2.4:1 to 7:1, from 2.4:1 to 6.6:1, from 2.4:1 to 6.2:1, from 2.4:1 to 5.8:1, from 2.4:1 to 5.4:1, from 2.4:1 to 5.1 :1, from 2.4:1 to 4.7:1, from 2.4:1 to 4.3:1, from 2.4:1 to 3.9:1, from 2.4:1 to 3.5:1, from 2.4:1 to 3.2:1, from 2.8:1 to 10:1, from 2.8:1 to 9.6:1, from 2.8:1 to 9.2:1, from 2.8:1 to 8.9:1, from 2.8:1 to 8.5:1, from 2.8:1 to 8.1 :1, from 2.8:1 to 7.7:1, from 2.8:1 to 7.3:1, from 2.8:1 to 7:1, from 2.8:1 to 6.6:1, from 2.8:1 to 6.2:1, from 2.8:1 to 5.8:1, from 2.8:1 to 5.4:1, from 2.8:1 to 5.1 :1, from 2.8:1 to 4.7:1, from 2.8:1 to 4.3:1, from 2.8:1 to 3.9:1, from 2.8:1 to 3.5:1, from 3.2:1 to 10:1, from 3.2:1 to 9.6:1, from 3.2:1 to 9.2:1, from 3.2:1 to 8.9:1, from 3.2:1 to 8.5:1, from 3.2:1 to 8.1 :1, from 3.2:1 to 7.7:1, from 3.2:1 to 7.3:1, from 3.2:1 to 7:1, from 3.2:1 to 6.6:1, from 3.2:1 to 6.2:1, from 3.2:1 to 5.8:1, from 3.2:1 to 5.4:1, from 3.2:1 to 5.1 :1, from 3.2:1 to 4.7:1, from 3.2:1 to 4.3:1, from 3.2:1 to 3.9:1, from 3.5:1 to 10:1, from 3.5:1 to 9.6:1, from 3.5:1 to 9.2:1, from 3.5:1 to 8.9:1, from 3.5:1 to 8.5:1, from 3.5:1 to 8.1 :1, from 3.5:1 to 7.7:1, from 3.5:1 to 7.3:1, from 3.5:1 to 7:1, from 3.5:1 to 6.6:1, from 3.5:1 to 6.2:1, from 3.5:1 to 5.8:1, from 3.5:1 to 5.4:1, from 3.5:1 to 5.1 :1, from 3.5:1 to 4.7:1, from 3.5:1 to 4.3:1, from 3.9:1 to 10:1, from 3.9:1 to 9.6:1, from 3.9:1 to 9.2:1, from 3.9:1 to 8.9:1, from 3.9:1 to 8.5:1, from 3.9:1 to 8.1 :1, from 3.9:1 to 7.7:1, from 3.9:1 to 7.3:1, from 3.9:1 to 7:1, from 3.9:1 to 6.6:1, from 3.9:1 to 6.2:1, from 3.9:1 to 5.8:1, from 3.9:1 to 5.4:1, from 3.9:1 to 5.1 :1, from 3.9:1 to 4.7:1, from 4.3:1 to 10:1, from 4.3:1 to 9.6:1, from 4.3:1 to 9.2:1, from 4.3:1 to 8.9:1, from 4.3:1 to 8.5:1, from 4.3:1 to 8.1 :1, from 4.3:1 to 7.7:1, from 4.3:1 to 7.3:1, from 4.3:1 to 7:1, from 4.3:1 to 6.6:1, from 4.3:1 to 6.2:1, from 4.3:1 to 5.8:1, from 4.3:1 to 5.4:1, from 4.3:1 to 5.1 :1, from 4.7:1 to 10:1, from 4.7:1 to 9.6:1, from 4.7:1 to 9.2:1, from 4.7:1 to 8.9:1, from 4.7:1 to 8.5:1, from 4.7:1 to 8.1 :1, from 4.7:1 to 7.7:1, from 4.7:1 to 7.3:1, from 4.7:1 to 7:1, from 4.7:1 to 6.6:1, from 4.7:1 to 6.2:1, from 4.7:1 to 5.8:1, from 4.7:1 to 5.4:1, from 5.1 :1 to 10:1, from 5.1 :1 to 9.6:1, from 5.1 :1 to 9.2:1, from 5.1 :1 to 8.9:1, from 5.1 :1 to 8.5:1, from 5.1 :1 to 8.1 :1, from 5.1 :1 to 7.7:1, from86261 -WO-PCT / DOW 86261 WO185.1 :1 to 7.3:1, from 5.1 :1 to 7:1, from 5.1 :1 to 6.6:1, from 5.1 :1 to 6.2:1, from 5.1 :1 to 5.8:1, from 5.4:1 to 10:1, from 5.4:1 to 9.6:1, from 5.4:1 to 9.2:1, from 5.4:1 to 8.9:1, from 5.4:1 to 8.5:1, from 5.4:1 to 8.1 :1, from 5.4:1 to 7.7:1, from 5.4:1 to 7.3:1, from 5.4:1 to 7:1, from 5.4:1 to 6.6:1, from 5.4:1 to 6.2:1, from 5.8:1 to 10:1, from 5.8:1 to 9.6:1, from 5.8:1 to 9.2:1, from 5.8:1 to 8.9:1, from 5.8:1 to 8.5:1, from 5.8:1 to 8.1 :1, from 5.8:1 to 7.7:1, from 5.8:1 to 7.3:1, from 5.8:1 to 7:1, from 5.8:1 to 6.6:1, from 6.2:1 to 10:1, from 6.2:1 to 9.6:1, from 6.2:1 to 9.2:1, from 6.2:1 to 8.9:1, from 6.2:1 to 8.5:1, from 6.2:1 to 8.1 :1, from 6.2:1 to 7.7:1, from 6.2:1 to 7.3:1, from 6.2:1 to 7:1, from 6.6:1 to 10:1, from 6.6:1 to 9.6:1, from 6.6:1 to 9.2:1, from 6.6:1 to 8.9:1, from 6.6:1 to 8.5:1, from 6.6:1 to 8.1 :1, from 6.6:1 to 7.7:1, from 6.6:1 to 7.3:1, from 7:1 to 10:1, from 7:1 to 9.6:1, from 7:1 to 9.2:1, from 7:1 to 8.9:1, from 7:1 to 8.5:1, from 7:1 to 8.1 :1, from 7:1 to 7.7:1, from 7.3:1 to 10:1, from 7.3:1 to 9.6:1, from 7.3:1 to 9.2:1, from 7.3:1 to 8.9:1, from 7.3:1 to 8.5:1, from 7.3:1 to 8.1 :1, from 7.7:1 to 10:1, from 7.7:1 to 9.6:1, from 7.7:1 to 9.2:1, from 7.7:1 to 8.9:1, from 7.7:1 to 8.5:1, from 8.1 :1 to 10:1, from 8.1 :1 to 9.6:1, from 8.1 :1 to 9.2:1, from 8.1 :1 to 8.9:1, from 8.5:1 to 10:1, from 8.5:1 to 9.6:1, from 8.5:1 to 9.2:1, from 8.9:1 to 10:1, from 8.9:1 to 9.6:1, or from 9.2:1 to 10:1. As used herein, the above ratio is a ratio of metal atoms and does not include non-metal components of compounds such as, for example, oxides or salts. In embodiments, the second metal may be rhenium. If the ratio is too high, cost may be prohibitively high; however, if the ratio is too low activity and selectivity may be reduced.

[0052] In one or more embodiments, the catalyst does not comprise boron.

[0053] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst in which the catalyst may have a surface area from between 20 m2 / g to 140 m2 / g. For instance, in embodiments the catalyst may have a surface area from between 20 m2 / g to 140 m2 / g, 20 m2 / g to 130 m2 / g, 20 m2 / g to 120 m2 / g, 20 m2 / g to 110 m2 / g, 20 m2 / g to 100 m2 / g, 20 m2 / g to 90 m2 / g, 20 m2 / g to 80 m2 / g, 20 m2 / g to 70 m2 / g, 20 m2 / g to 60 m2 / g, 20 m2 / g to 50 m2 / g, 20 m2 / g to 40 m2 / g, 20 m2 / g to 30 m2 / g, 30 m2 / g to 140 m2 / g, 30 m2 / g to 130 m2 / g, 30 m2 / g to 120 m2 / g, 30 m2 / g to 110 m2 / g, 30 m2 / g to 100 m2 / g, 30 m2 / g to 90 m2 / g, 30 m2 / g to 80 m2 / g, 30 m2 / g to 70 m2 / g, 30 m2 / g to 60 m2 / g, 30 m2 / g to 50 m2 / g, 30 m2 / g to 40 m2 / g, 40 m2 / g to 140 m2 / g, 40 m2 / g to 130 m2 / g, 40 m2 / g to 120 m2 / g, 40 m2 / g to 110 m2 / g, 40 m2 / g to 100 m2 / g, 40 m2 / g to 90 m2 / g, 40 m2 / g to 80 m2 / g, 40 m2 / g to 70 m2 / g, 40 m2 / g to 60 m2 / g, 40 m2 / g to 50 m2 / g, 50 m2 / g to 140 m2 / g, 50 m2 / g to 130 m2 / g, 50 m2 / g to 120 m2 / g, 50 m2 / g to 11086261 -WO-PCT / DOW 86261 WO19 m2 / g, 50 m2 / g to 100 m2 / g, 50 m2 / g to 90 m2 / g, 50 m2 / g to 80 m2 / g, 50 m2 / g to 70 m2 / g, 50 m2 / g to 60 m2 / g, 60 m2 / g to 140 m2 / g, 60 m2 / g to 130 m2 / g, 60 m2 / g to 120 m2 / g, 60 m2 / g to 110 m2 / g, 60 m2 / g to 100 m2 / g, 60 m2 / g to 90 m2 / g, 60 m2 / g to 80 m2 / g, 60 m2 / g to 70 m2 / g, 70 m2 / g to 140 m2 / g, 70 m2 / g to 130 m2 / g, 70 m2 / g to 120 m2 / g, 70 m2 / g to 110 m2 / g, 70 m2 / g to 100 m2 / g, 70 m2 / g to 90 m2 / g, 70 m2 / g to 80 m2 / g, 80 m2 / g to 140 m2 / g, 80 m2 / g to 130 m2 / g, 80 m2 / g to 120 m2 / g, 80 m2 / g to 110 m2 / g, 80 m2 / g to 100 m2 / g, 80 m2 / g to 90 m2 / g, 90 m2 / g to 140 m2 / g, 90 m2 / g to 130 m2 / g, 90 m2 / g to 120 m2 / g, 90 m2 / g to 110 m2 / g, 90 m2 / g to 100 m2 / g, 100 m2 / g to 140 m2 / g, 100 m2 / g to 130 m2 / g, 100 m2 / g to 120 m2 / g, 100 m2 / g to 110 m2 / g, 110 m2 / g to 140 m2 / g, 110 m2 / g to 130 m2 / g, 110 m2 / g to 120 m2 / g, 120 m2 / g to 140 m2 / g, 120 m2 / g to 130 m2 / g, or 130 m2 / g to 140 m2 / g. If the catalyst surface area is too high, fabrication may be difficult; however, if the catalyst surface area is too low, catalyst activity may be low and selectivity of EDA may be reduced.

[0054] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst in which the catalyst may comprise a carrier, in which the carrier may have a surface area from between 30 m2 / g to 450 m2 / g. For instance, in embodiments the carrier may have a surface area from between 30 m2 / g to 450 m2 / g, 50 m2 / g to 450 m2 / g, 100 m2 / g to 450 m2 / g, 150 m2 / g to 450 m2 / g, 200 m2 / g to 450 m2 / g, 250 m2 / g to 450 m2 / g, 300 m2 / g to 450 m2 / g, 350 m2 / g to 450 m2 / g, 400 m2 / g to 450 m2 / g, 30 m2 / g to 400 m2 / g, 50 m2 / g to 400 m2 / g, 100 m2 / g to 400 m2 / g, 150 m2 / g to 400 m2 / g, 200 m2 / g to 400 m2 / g, 250 m2 / g to 400 m2 / g, 300 m2 / g to 400 m2 / g, 350 m2 / g to 400 m2 / g, 30 m2 / g to 350 m2 / g, 50 m2 / g to 350 m2 / g, 100 m2 / g to 350 m2 / g, 150 m2 / g to 350 m2 / g, 200 m2 / g to 350 m2 / g, 250 m2 / g to 350 m2 / g, 300 m2 / g to 350 m2 / g, 30 m2 / g to 300 m2 / g, 50 m2 / g to 300 m2 / g, 100 m2 / g to 300 m2 / g, 150 m2 / g to 300 m2 / g, 200 m2 / g to 300 m2 / g, 250 m2 / g to 300 m2 / g, 30 m2 / g to 250 m2 / g, 50 m2 / g to 250 m2 / g, 100 m2 / g to 250 m2 / g, 150 m2 / g to 250 m2 / g, 200 m2 / g to 250 m2 / g, 30 m2 / g to 200 m2 / g, 50 m2 / g to 200 m2 / g, 100 m2 / g to 200 m2 / g, 150 m2 / g to 200 m2 / g, 30 m2 / g to 150 m2 / g, 50 m2 / g to 150 m2 / g, 100 m2 / g to 150 m2 / g, 30 m2 / g to 100 m2 / g, 50 m2 / g to 100 m2 / g, 30 m2 / g to 50 m2 / g. If the carrier surface area is too high, selectivity to the desired ethyleneamines may be low; however, if the carrier surface area is too low, metal dispersion may be poor and activity and selectivity of the desired ethyleneamines may be low.

[0055] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed86261 -WO-PCT / DOW 86261 WO20 stream, to a catalyst comprising an active component that is from 3 wt. % to 40 wt. %, based on the total weight of the catalyst.. For instance, in embodiments the catalyst may comprise from 3 wt. % to 40 wt. %, from 3 wt. % to 35 wt. %, from 3 wt. % to 30 wt. %, from 3 wt. % to 25 wt. %, from 3 wt. % to 20 wt. %, from 3 wt. % to 15 wt. %, from 3 wt. % to 10 wt. %, from 1 wt. % to 5 wt. %, from 5 wt. % to 40 wt. %, from 5 wt. % to 35 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 10 wt. %, from 10 wt. % to 40 wt. %, from 10 wt. % to 35 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 25 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 15 wt. %, from 15 wt. % to 40 wt. %, from 15 wt. % to 35 wt. %, from 15 wt. % to 30 wt. %, from 15 wt. % to 25 wt. %, from 15 wt. % to 20 wt. %, from 20 wt. % to 40 wt. %, from 20 wt. % to 35 wt. %„ from 20 wt. % to 30 wt. %, from 20 wt. % to 25 wt. %, from 30 wt. % to 40 wt. %, from 30 wt. % to 35 wt. %, or from 35 wt. % to 40 wt. % total active component. If the active component is too high, dispersion may be poor, reducing activity and selectivity; however, if the active component is too low, activity and conversion may be reduced.

[0056] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst that comprises from 2 wt. % to 30 wt. % nickel, based on the total weight of the catalyst. For instance, in embodiments the catalyst may comprise nickel in amounts from 2 wt. % to 30 wt. %, from 2 wt. % to 25 wt. %, from 2 wt. % to 20 wt. %, from 2 wt. % to 10 wt. %, from 2 wt. % to 5 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 10 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 25 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 15 wt. %, from 15 wt. % to 30 wt. %, from 15 wt. % to 25 wt. %, from 15 wt. % to 20 wt. %, from 20 wt. % to 30 wt. %, from 20 wt. % to 25 wt. %, or from 25 wt. % to 30 wt. % of the total catalyst. If the amount of nickel is too high, dispersion may be poor, reducing activity and selectivity; however, if the amount of nickel is too low, catalytic activity may be reduced.

[0057] In embodiments, a catalyst may comprise from 0.5 wt. % to 5 wt. % rhenium, based on the total weight of the catalyst (active components and carrier components). For instance, in embodiments the mass of rhenium may be from 0.5 wt. % to 5.0 wt.%, from 0.5 wt. % to 4.5 wt.%, from 0.5 wt.% to 4.0 wt.%, from 0.5 wt. % to 3.5 wt.%, from 0.5 wt.% to 3.0 wt.%, from 0.5 wt.% to 2.5 wt.%, from 0.5 wt.% to 2.0 wt.%, from 0.5 wt.% to 1.5 wt. %, from 0.5 wt. % to 1.0 wt. %, from 1.0 wt. % to 5.0 wt. %, from 1.0 wt. % to 4.5 wt. %, from 1.0 wt. % to 4.086261 -WO-PCT / DOW 86261 WO21 wt. %, from 1.0 wt. % to 3.5 wt. %, from 1.0 wt. % to 3.0 wt. %, from 1.0 wt. % to 2.5 wt. %, from 1.0 wt. % to 2.0 wt. %, from 1.0 wt. % to 1.5 wt. %, from 1.5 wt.% to 5.0 wt. %, from 1.5 wt.% to 4.5 wt.%, from 1.5 wt.% to 4.0 wt.%, from 1.5 wt.% to 3.5 wt.%, from 1.5 wt.% to 3.0 wt.%, from 1.5 wt.% to 2.5 wt.%, from 1.5 wt.% to 2.0 wt.%, from 2.0 wt.% to 5.0 wt.%, from 2.0 wt.% to 4.5 wt.%, from 2.0 wt.% to 4.0 wt.%, from 2.0 wt.% to 3.5 wt.%, from 2.0 wt.% to 3.0 wt.%, from 2.0 wt.% to 2.5 wt.%, from 2.5 wt.% to 5.0 wt.%, from 2.5 wt.% to 4.5 wt.%, from 2.5 wt.% to 4.0 wt.%, from 2.5 wt.% to 3.5 wt.%, from 2.5 wt.% to 3.0 wt.%, from 3.0 wt.% to 5.0 wt.%, from 3.0 wt.% to 4.5 wt.%, from 3.0 wt.% to 4.0 wt.%, from 3.0 wt.% to 3.5 wt.%, from 3.5 wt.% to 5.0 wt.%, from 3.5 wt.% to 4.5 wt.%, from 3.5 wt.% to 4.0 wt.%, from 4.0 wt.% to 5.0 wt.%, from 4.0 wt.% to 4.5 wt.%, or from 4.5 wt.% to 5.0 wt.% based on the total mass of the catalyst. If the mass of rhenium is too high, the manufacturing cost may increase without increase in selectivity to the desired ethyleneamines; however, if the mass of rhenium is too low, the selectivity to the desired ethyleneamine may be low.

[0058] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream, the recycle stream, and hydrogen, which may be included in the feed stream, to a catalyst that comprises from 0.5 wt. % to 5 wt. % niobium, based on the total weight of the catalyst (active components and carrier components). For instance, in embodiments the mass of niobium may be from 0.5 wt. % to 5.0 wt.%, from 0.5 wt. % to 4.5 wt.%, from 0.5 wt.% to 4.0 wt.%, from 0.5 wt. % to 3.5 wt.%, from 0.5 wt.% to 3.0 wt.%, from 0.5 wt.% to 2.5 wt.%, from 0.5 wt.% to 2.0 wt.%, from 0.5 wt.% to 1.5 wt. %, from 0.5 wt. % to 1.0 wt. %, from 1.0 wt. % to 5.0 wt. %, from 1.0 wt. % to 4.5 wt. %, from 1.0 wt. % to 4.0 wt. %, from 1.0 wt. % to3.5 wt. %, from 1.0 wt. % to 3.0 wt. %, from 1.0 wt. % to 2.5 wt. %, from 1.0 wt. % to 2.0 wt. %, from 1.0 wt. % to 1.5 wt. %, from 1.5 wt.% to 5.0 wt. %, from 1.5 wt.% to 4.5 wt.%, from1.5 wt.% to 4.0 wt.%, from 1.5 wt.% to 3.5 wt.%, from 1.5 wt.% to 3.0 wt.%, from 1.5 wt.% to2.5 wt.%, from 1.5 wt.% to 2.0 wt.%, from 2.0 wt.% to 5.0 wt.%, from 2.0 wt.% to 4.5 wt.%, from 2.0 wt.% to 4.0 wt.%, from 2.0 wt.% to 3.5 wt.%, from 2.0 wt.% to 3.0 wt.%, from 2.0 wt.% to 2.5 wt.%, from 2.5 wt.% to 5.0 wt.%, from 2.5 wt.% to 4.5 wt.%, from 2.5 wt.% to 4.0 wt.%, from 2.5 wt.% to 3.5 wt.%, from 2.5 wt.% to 3.0 wt.%, from 3.0 wt.% to 5.0 wt.%, from 3.0 wt.% to 4.5 wt.%, from 3.0 wt.% to 4.0 wt.%, from 3.0 wt.% to 3.5 wt.%, from 3.5 wt.% to 5.0 wt.%, from 3.5 wt.% to 4.5 wt.%, from 3.5 wt.% to 4.0 wt.%, from 4.0 wt.% to 5.0 wt.%, from 4.0 wt.% to 4.5 wt.%, or from 4.5 wt.% to 5.0 wt.% based on the total mass of the catalyst. If the mass of niobium is too high, the manufacturing cost may increase without increase in86261 -WO-PCT / DOW 86261 WO22 selectivity to the desired ethyleneamines; however, if the mass of niobium is too low, the selectivity to the desired ethyleneamine may be low.

[0059] Heterogeneous catalyst preparation commonly comprises incipient wetness impregnation, which is the most widely used method due to preparation simplicity, low costs, and limited amount of waste. Metal loading of incipient wetness impregnation is a function of the amount of active precursor or precursors based on solvent solubility. Incipient wetness impregnation is a traditional impregnation method that impregnates a carrier with one or more metal salts, which are precursors to metal catalysts. Often, the impregnation includes contacting a carrier with an aqueous solution formed from a mixture of metal salts to form an impregnated carrier. The impregnated carrier may then be calcined and reduced by known methods. However, it was discovered that mixing an aqueous niobium-containing salt solution to a salt comprising the first metal and / or the second metal, as described herein, in aqueous solution resulted in precipitation. This precipitation for a traditional incipient wetness impregnation method is problematic and can lead to lower metal dispersions and a less than desired metal loading for the catalyst.

[0060] It was discovered that the metal contents achieved in embodiments described hereinabove could not be achieved by a traditional incipient wetness technique. In embodiments, to obtain the desired metal content in the catalysts, the catalysts are formed by unique impregnation methods disclosed herein.

[0061] In embodiments, a method for impregnation for preparing a catalyst comprises an initial impregnation, an initial calcining, a subsequent impregnation, a subsequent calcining, a reduction, cooling, and passivating. In embodiments, the initial impregnation step comprises contacting a carrier composite with an aqueous solution comprising the third metal to form a first impregnated carrier composite. In embodiments, the initial calcining comprises calcining the first impregnated carrier composite, thereby forming a first doped carrier. In embodiments, the subsequent impregnation step comprises contacting the first doped carrier with an aqueous solution comprising the first metal and the second metal to form a second impregnated carrier composite. In embodiments, the subsequent calcining comprises calcining the second impregnated carrier composite, thereby forming the second doped carrier. In embodiments, the second doped carrier is reduced by contacting the second doped carrier with a hydrogen flow, resulting in an unpassivated catalyst. In embodiments, the unpassivated catalyst is cooled and passivated to result in a catalyst.86261 -WO-PCT / DOW 86261 WO23

[0062] In embodiments, a method for impregnation for preparing a catalyst comprises an initial impregnation, an initial calcining, a subsequent impregnation, a subsequent calcining, a reduction, cooling, and passivating. In embodiments, the initial impregnation step comprises contacting a carrier composite with an aqueous solution comprising only one of the first, the second, or the third metal to form a first impregnated carrier composite. In embodiments, the initial calcining comprises calcining the first impregnated carrier composite, thereby forming a first doped carrier. In embodiments, the subsequent impregnation step comprises a second impregnation step comprising contacting the first doped carrier with an aqueous solution comprising only one of the first, the second, or the third metal, but a metal different than the metal used in the first impregnation to form a second impregnated carrier composite. In embodiments the subsequent calcining comprises calcining the second impregnated carrier composite, thereby forming a second doped carrier. In embodiments, the method further comprises an additional impregnation after the subsequent impregnation. The additional impregnation step comprises contacting the second doped carrier with an aqueous solution comprising one of the first, the second, or the third metal, but a metal different than that use in the initial impregnation and the subsequent impregnation, to form a third impregnated carrier composite. In embodiments, an additional calcining after the additional impregnation step is performed. In embodiments, the additional calcining comprises calcining the third impregnated carrier, thereby forming a third doped carrier. In embodiments, the third doped carrier is reduced by contacting the third doped carrier with hydrogen to form an unpassivated catalyst. In embodiments, the unpassivated catalyst is cooled and passivated to result in a catalyst.

[0063] In embodiments, a method for impregnating for preparing a catalyst comprises an initial impregnation, an initial calcining, a subsequent impregnation, a subsequent calcining, a reduction, cooling, and passivating. In embodiments, the initial impregnation step comprises contacting a carrier composite with an aqueous solution comprising the first metal and the second metal to form a first impregnated carrier composite. In embodiments, the initial calcining comprises calcining the first impregnated carrier composite, thereby forming the first doped carrier. In embodiments, the subsequent impregnation step comprises contacting the first doped carrier with an aqueous solution comprising the third metal to form a second impregnated carrier composite. In embodiments, the subsequent calcining comprises calcining the first impregnated carrier composite, thereby forming the second doped carrier. In embodiments, the second doped carrier is reduced by contacting the second doped carrier with hydrogen , to form an86261 -WO-PCT / DOW 86261 WO24 unpassivated catalyst. In embodiments, the unpassivated catalyst is cooled and passivated to result in a catalyst.

[0064] In embodiments, the method for preparing a catalyst comprising a carrier composite preparation step, an initial impregnation step, an initial calcining step, a subsequent impregnation step, a subsequent calcining step, an additional impregnation step, an additional calcining step, a reduction step, a cooling step, and a passivation step is performed greater than once to achieve maximum metal content in the catalyst.

[0065] In embodiments, the method for preparing a catalyst comprising a carrier composite preparation step, an initial impregnation step, an initial calcining step, a subsequent impregnation step, a subsequent calcining step, a reduction step, a cooling step, and a passivation step is performed greater than once to achieve maximum metal content in the catalyst.

[0066] In embodiments, a method for preparing a catalyst comprises a drying step, wherein the drying step comprises heating a carrier to remove moisture. In embodiment, the drying method occurs prior to initial impregnation. In embodiments, the drying method occurs prior to subsequent impregnation. In embodiments, the drying method occurs prior to additional impregnation. In embodiments, the drying method occurs prior to calcining. In embodiments, the drying step may be performed at from 70 ° C to 200 ° C, for a duration of 2 to 72 hours.

[0067] For example, in embodiments, the drying temperature may be from 70 ° C to 200 ° C, from 70 ° C to 150 ° C, from 70 ° C to 100 ° C, from 100 ° C to 200 ° C, from 100 ° C to 150 ° C, from 150 ° C to 250 ° C. For example, in embodiments, the heat treatment duration may be from 2 to 72 hours, from 5 to 50 hours, from 5 to 30 hours, from 5 to 10 hours, from 20 to 72 hours, from 20 to 50 hours, from 20 to 30 hours, from 30 to 72 hours, from 30 to 50 hours, from 50 hours to 70 hours, or from 60 hours to 70 hours.

[0068] In embodiments of each of the impregnation methods described above, the reduction is conducted by contacting a doped carrier with a hydrogen containing gas at a flow rate from 30 to 60 Standard Liters Per Hour (SLPH), at a temperature from 250 °C to 650 °C, for a duration of 0.5 to 5 hours. For example, in embodiments, the flow rate may be from 30 to 50 SLPH, from 30 to 40 SLPH, from 40 to 50 SLPH, from 40 to 60 SLPH, or from 50 to 60 SLPH. For example, in embodiments, the reducing temperature may be from 250 °C to 600 °C, from 250 °C to 400 °C, from 300 °C to 650 °C, from 300 °C to 400 °C, from 350 °C to 650, from 350 °C to 400, or from 550 °C to 650. For example, in embodiments, the reducing duration may be from 0.5 to 4 hours, from 0.5 to 3 hours, from 0.5 to 2 hours, from 0.5 to 1 hours, from 1 to 5 hours,86261 -WO-PCT / DOW 86261 WO25 from 1 to 4 hours, from 1 to 3 hours, from 1 to 2 hours, from 2 to 5 hours, from 2 to 4 hours, from 2 to 3 hours, from 3 to 5 hours, from 3 to 4 hours, or from 4 to 5 hours. In one or more embodiment, the doped carrier is the second doped carrier. In one or more embodiment, the doped carrier is the third doped carrier. In one or more embodiments, the hydrogen containing gas is substantially pure H2.

[0069] In embodiments of each of the impregnation methods described above, the calcining is conducted at a temperature from 300 °C to 500 ° C. For example, in embodiments, the calcining temperature may be from 300 °C to 450 °C, from 300 °C to 400 °C, or from 450 °C to 500 °C.

[0070] In embodiments an aqueous solution is formed by dissolving ammonium niobate (V) oxalate hydrate in water.

[0071] In embodiments, a process for producing amines by reductive amination may comprise a selectivity of EDA in the product composition (not including unreacted MEA) from 50% to 99%. For example, selectivity of EDA may be from 50% to 95%, from 50% to 90%, from 50% to 85%, from 50% to 80%, from 50% to 75%, from 50% to 70%, from 50% to 65%, from 50% to 60%, from 50% to 55%, from 55% to 99%, from 55% to 95%, from 55% to 90%, from 55% to 85%, from 55% to 80%, from 55% to 75%, from 55% to 70%, from 55% to 65%, from 55% to 60%, from 60% to 99%, from 60% to 95%, from 60% to 90%, from 60% to 85%, from 60% to 80%, from 60% to 75%, from 60% to 70%, from 60% to 65%, from 65% to 99%, from 65% to 95%, from 65% to 90%, from 65% to 85%, from 65% to 80%, from 65% to 75%, from 65% to 70%, from 70% to 99%, from 70% to 95%, from 70% to 90%, from 70% to 85%, from 70% to 80%, from 70% to 75%, from 75% to 99%, from 75% to 95%, from 75% to 90%, from 75% to 85%, from 75% to 80%, from 80% to 99%, from 80% to 95%, from 80% to 90%, from 80% to 85%, from 85% to 99%, from 85% to 95%, from 85% to 90%, from 90% to 99%, from 90% to 95%, or from 95% to 99%.

[0072] In embodiments, the amount of NEED A in the product effluent is from 1 ppm to 13000 ppm. For example, the concentration of NEEDA in the effluent may be from 1 ppm to 12000 ppm, from 1 ppm to 10000 ppm, from 1 ppm to 8000 ppm, from 1 ppm to 6000 ppm, from 1 ppm to 4000 ppm, from 1 ppm to 2000 ppm, from 1 ppm to 1000 ppm, from 1 ppm to 450 ppm, from 450 ppm to 13000 ppm, from 450 ppm to 12000 ppm, from 450 ppm to 10000 ppm, from 450 ppm to 8000 ppm, from 450 ppm to 6000 ppm, from 450 ppm to 4000 ppm, from 450 ppm to 2000 ppm, from 450 ppm to 1000 ppm, from 1000 ppm to 13000 ppm, from 1000 ppm to 12000 ppm, from 1000 ppm to 10000 ppm, from 1000 ppm to 8000 ppm, from 1000 ppm to86261 -WO-PCT / DOW 86261 WO266000 ppm, from 1000 ppm to 4000 ppm, from 1000 ppm to 2000 ppm, from 2000 ppm to 13000 ppm, from 2000 ppm to 12000 ppm, from 2000 ppm to 10000 ppm, from 2000 ppm to 8000 ppm, from 2000 ppm to 6000 ppm, from 2000 ppm to 5000 ppm, from 2000 ppm to 4000 ppm, from 4000 ppm to 13000 ppm, from 4000 ppm to 12000 ppm, from 4000 ppm to 10000 ppm, from 4000 ppm to 8000 ppm, from 4000 ppm to 6000 ppm, from 6000 ppm to 13000 ppm, from 6000 ppm to 12000 ppm, from 6000 ppm to 10000 ppm, from 6000 ppm to 8000 ppm, from 8000 ppm to 13000 ppm, from 8000 ppm to 12000 ppm, from 8000 ppm to 10000 ppm, from 10000 ppm to 13000 ppm, from 8000 ppm to 12000 ppm, from 8000 ppm to 10000 ppm, from 10000 ppm to 13000 ppm, or from 10000 ppm to 12000 ppm.

[0073] In embodiments, the amount of NMEDA in the product effluent is from 1 ppm to 13000 ppm. For example, the concentration of NMEDA in the effluent may be from 1 ppm to 12000 ppm, from 1 ppm to 10000 ppm, from 1 ppm to 8000 ppm, from 1 ppm to 6000 ppm, from 1 ppm to 4000 ppm, from 1 ppm to 2000 ppm, from 1 ppm to 1000 ppm, from 1 ppm to 450 ppm, from 450 ppm to 13000 ppm, from 450 ppm to 12000 ppm, from 450 ppm to 10000 ppm, from 450 ppm to 8000 ppm, from 450 ppm to 6000 ppm, from 450 ppm to 4000 ppm, from 450 ppm to 2000 ppm, from 450 ppm to 1000 ppm, from 1000 ppm to 13000 ppm, from 1000 ppm to 12000 ppm, from 1000 ppm to 10000 ppm, from 1000 ppm to 8000 ppm, from 1000 ppm to 6000 ppm, from 1000 ppm to 4000 ppm, from 1000 ppm to 2000 ppm, from 2000 ppm to 13000 ppm, from 2000 ppm to 12000 ppm, from 2000 ppm to 10000 ppm, from 2000 ppm to 8000 ppm, from 2000 ppm to 6000 ppm, from 2000 ppm to 5000 ppm, from 2000 ppm to 4000 ppm, from 4000 ppm to 13000 ppm, from 4000 ppm to 12000 ppm, from 4000 ppm to 10000 ppm, from 4000 ppm to 8000 ppm, from 4000 ppm to 6000 ppm, from 6000 ppm to 13000 ppm, from 6000 ppm to 12000 ppm, from 6000 ppm to 10000 ppm, from 6000 ppm to 8000 ppm, from 8000 ppm to 13000 ppm, from 8000 ppm to 12000 ppm, from 8000 ppm to 10000 ppm, from 10000 ppm to 13000 ppm, from 8000 ppm to 12000 ppm, from 8000 ppm to 10000 ppm, from 10000 ppm to 13000 ppm, or from 10000 ppm to 12000 ppm.

[0074] Without intending to be bound by any particular theory, it is believed the process described herein may be used for reductive amination and producing a product having a lesser amount of NEMDA, NEEDA, MA, and EA, compared to methods using conventional catalysts.86261 -WO-PCT / DOW 86261 WO27EXAMPLES

[0075] The various embodiments disclosed herein will be further clarified by the following examples. The examples are illustrative in nature, and should not be understood to limit the embodiments disclosed herein.Catalyst Example 1 Preparation

[0076] Catalyst Example 1 is formed from a carrier component and an active component. A precursor salt of each respective metal was dissolved in distilled water to form an impregnation solution. In each case, the carrier was impregnated with the metal solution to incipient wetness and gently agitated until all the liquid had been adsorbed. The manufacture of Catalyst Example 1 comprises a carrier composite preparation step, a first impregnation step, a first calcining step, a second impregnation step, a second calcining step, a reduction step, a cooling step, and a passivation step. A detailed description of the catalyst preparation steps may be reviewed in patent EP 0737514 Al.CARRIER COMPONENT

[0077] The preparation of a carrier composite of this example is carried out in the manner described in patent EP 0737669 Al, which is incorporated herein by reference, in which the preparation comprises drying the carrier composite at 70 °C for 24 hr to remove excess moisture. The carrier component of the present example comprises 80 wt. % alumina and 20 wt. % silica. The carrier component of the present example is comprised of 1 / 8” diameter extrudates.ACTIVE COMPONENT

[0078] The active component of Catalyst Example 1 comprises nickel as the first metal of the active component. The second metal of the active component in Catalyst Example 1 is rhenium. The third metal of the active component in Catalyst Example 1 is niobium. In order to manufacture a catalyst comprising a carrier component and an active component, an impregnation step may be included. Each active component is impregnated into the carrier component by an impregnation step to manufacture Catalyst Example 1.First Impregnation and First Calcining

[0079] The third metal of the active component, niobium, was introduced to the carrier solution in the first impregnation step. Specifically, an aqueous solution of ammonium niobate (V) oxalate hydrate was prepared by dissolving 5.54 g ammonium niobate (V) oxalate hydrate86261 -WO-PCT / DOW 86261 WO28(product number 525839 from MilliporeSigma) in deionized water in a first vessel. A second vessel was charged with 151 g of the carrier. The contents of the first vessel was transferred to the second vessel to allow contact between the aqueous ammonium niobate (V) oxalate hydrate with the carrier to create the first impregnated carrier.

[0080] To remove residual impurities or volatile substances and promote thermal decomposition of the niobium salt from the first impregnated carrier, the first impregnated carrier was calcined in air at 340 °C for 3 hours, resulting in a first doped carrier.Second Impregnation and Second Calcining

[0081] The first metal of the active component, nickel, was introduced to the carrier solution in the second impregnation step. Additionally, the second metal of the active component, rhenium, was introduced to the carrier solution in the second impregnation step. Specifically, an aqueous solution of nickel nitrate hexahydrate and ammonium perrhenate was prepared by dissolving 69.01 g nickel nitrate hexahydrate (product number 203874 from MilliporeSigma) and dissolving 5.14 g ammonium perrhenate (product number 316954 from MilliporeSigma) in deionized water in a first vessel. A second vessel was charged with the first doped carrier. The contents of the first vessel was transferred to the second vessel to allow contact between the aqueous nickel nitrate hexahydrate and the aqueous ammonium perrhenate with the first doped carrier to create a second impregnation carrier.

[0082] To remove residual impurities or volatile substances and promote thermal decomposition of the nickel and rhenium salts from the second impregnation carrier, the second impregnation carrier was calcined in air at 340 °C for 3 hours, resulting in a second doped carrier.Reduction

[0083] A reduction in part of the doped metals was instigated on the second doped carrier under hydrogen flow and heat. The second doped carrier was contacted with a hydrogen flow at 340 °C. The hydrogen flowed at 41.6 SLPH for 3 hours. The reduction of the second doped carrier resulted in an unpassivated Experiment 1 catalyst.Cooling

[0084] The unpassivated Experiment 1 catalyst was cooled to below 100 °C in hydrogen. After cooling to below 100 °C, the catalyst was further cooled under nitrogen.86261 -WO-PCT / DOW 86261 WO29Passivation

[0085] Catalyst passivation refers to the formation of a protective oxide layer on the active metal particles that prevent their oxidation when exposed to air, stabilizing the catalyst. The unpassivated Experiment 1 catalyst was passivated by exposing the catalyst to a mixture of oxygen and nitrogen at room temperature. Approximately 180 seem (standard cubic centimeters) of 5% O2 / N2 and 420 seem of N2 were introduced to the catalyst until the exotherm peaked and then cooled to room temperature. At no time was the exotherm allowed to exceed 70 °C.

[0086] The carrier composite preparation step, the first impregnation step, the first calcining step, the second impregnation step, the second calcining step, the reduction step, the cooling step, and the passivation step were repeated until approximately 500 g of catalyst was generated. Each series of steps using approximately 150 g carrier component will yield approximately 170 g catalyst material.

[0087] Catalyst Example 1 carrier component is 80 wt. % alumina and 20 wt. % silica. Catalyst Example 1 active components mass to the total catalyst weight (carrier component and active component) is 8.2 wt. % nickel, 2.1 wt. % rhenium, and 1.0 wt. % niobium. The Catalyst Example 1 surface area is 110 m2 / g. Catalyst Example 1 is a solid particle extrudate of 1 / 8” diameter.Comparative Catalyst Example A Preparation

[0088] Comparative Catalyst Example A comprises boron, nickel, and rhenium. Comparative Catalyst Example A comprises a carrier component and an active component. A detailed description of the catalyst preparation steps may be reviewed in patent EP 0737514 Al.

[0089] The preparation of a carrier composite of this example is carried out in the manner described in patent EP 0737669 Al. The carrier component is 80 wt. % alumina and 20 wt. % silica. The active components mass to the total catalyst weight (carrier component and active component) is 8.2 wt. % nickel, 2.1 wt. % rhenium, and 1.6 wt. % boron. The Comparative Catalyst Example A surface area is 107 m2 / g (as described in WO2001066247 A2). Comparative Catalyst Example A is a solid particle extrudates of 1 / 8” diameter.REACTION PERFORMANCE EXAMPLES

[0090] Reaction Examples 1 to 6 and Comparative Reaction Examples A to F analyze a variety of conditions to compare the performance of each of the catalysts described herein. The results favor a mass-based approximation to selectivity rather than a molar formula often described in86261 -WO-PCT / DOW 86261 WO30 textbooks. This approach is used for easier comparison with mass-based production ratios calculated by technical centers and production personnel. All mass-based selectivities reported herein use the mass-based definition given below.[L0091

[0092] Similarly, conversion is presented on a weight basis, wherein conversion refers specifically to the conversion of MEA in the influent stream. Mass conversion of MEA may be calculated by the below formula.. wt% of MEA in the feed-wt% of MEA in the product

[0093] MEA Conversion = - wt% of MEA in the feed x 100Reaction Conditions

[0094] The main properties of effluent stream resulting from Catalyst Example 1 and Comparative Catalyst Example A, respectively, were characterized by gas chromatography (GC) among other techniques, as described below. The reaction performances were evaluated in a 1 inch by 8 foot up-flow, heterogeneous catalyst packed bed reactor with a tubular reaction zone containing the catalyst. The reactor bed is made of 0.81 inch inner diameter seamless Swagelok tubing.

[0095] For each respective run, the reactor was packed with the respective catalyst. Any material inside of the reactor was removed prior to each reaction run. Catalyst Example 1 tests were performed after packing a reactor with 400 g Catalyst Example 1. Comparative Catalyst Example A tests were performed after packing the reactor with 400 g Comparative Catalyst Example A. The feed material was 99 percent pure MEA (from Dow Chemical Company) and ammonia (from Airgas). The MEA was pumped in a continuous, uninterrupted flow from two 500 mL ISCO syringe pumps. The MEA feed stream passed through a pre-heater before entering the reactor. MA and EA were added to simulate a recycle stream. The MA stream was pumped into the feed line in the bottom of the reactor in a continuous, uninterrupted flow from a single ISCO pump with a backpressure regulator set at 500 psig to keep the upstream fluid in liquid form. A capillary tube combined with a differential pressure sensor was installed in the downstream of the MA stream to monitor the flow rate. A flow of 99 percent pure anhydrous MA (from Eastman) was used to control the concentration of MA. A 70 wt. % aqueous EA solution (from Eastman) stream was pumped into the feed line in the bottom of the reactor in a continuous, uninterrupted flow from a single ISCO pump with a backpressure regulator set at 500 psig to keep the upstream fluid in liquid form. A capillary tube combined with a differential86261 -WO-PCT / DOW 86261 WO31 pressure sensor was installed in the downstream of the EA stream to monitor the flow rate. The flow of EA was used to control the concentration of EA. Before entering the reactor, a separate stream of hydrogen gas and ammonia contact the MEA feed stream. The hydrogen was supplied from a 6000 psi hydrogen cylinder. The ammonia supply was supplied from 500 psi ammonia cylinders. The ammonia was pumped into the MEA stream in a continuous, uninterrupted flow from two 500 mL ISCO syringe pumps. The reductive amination reaction examples were conducted in a temperature range of 157-177 °C. in the reactor conditions at Reaction 1 to 12 are summarized in Table 1. Reactions 1 to 12 generate the data used to compare Comparative Catalyst A to Example Catalyst 1 performance with respect to reduction of NMEDA and NEEDA. Concentration of the Light Alkylamine in Table 1 may be defined as the mass of light alkylamine divided by the mass of ammonia.

[0096] Table 1. Reactions 1 to 12 were performed at 1900 psig, 50 SLPH (Standard Liter Per Hour) H2, hydrogen concentration at 4 mol. %, MEA flow rate at 10.3 mL / min, MEA SV at 25.6 mol / hr-kg cat, and NH3 flow at 17.1 mL per minute under the light alkylamine type, alkylamine concentration, alkylamine flow, and MEA conversion conditions.86261 -WO-PCT / DOW 86261 WO32Catalyst Performance in NMEDA Generation

[0097] FIG. 1 is a bar graph of data using simulated recycle stream from Reactions 1 to 3 and Reactions 7 to 9, wherein the NMEDA formed in product mixtures over Comparative Catalyst Example A and Catalyst Example 1 at the MA feed concentrations of 5,000 ppm (Reaction 1 and Reaction 7), 12,500 ppm (Reaction 2 and Reaction 8), and 20,000 ppm (Reaction 3 and Reaction 9) in the feed stream are used to evaluate performance. The weight percentage of NMEDA in the product mixtures increased as the MA concentrations in the feed stream increased. These results are expected since, like NH3, MA can react with MEA by reductive amination to form NMEDA, and the rate of NMEDA formation increases when MA reactant concentration increases. At each MA level, the NMEDA generated in product mixtures over the two catalysts were similar, with approximately 0.015 wt. % difference (absolute). The Catalyst Example 1 formed less NMEDA than Comparative Catalyst Example A at medium and high feed levels, while the Catalyst Experiment 1 formed less NMEDA than Comparative Catalyst Example A at low MA levels.Catalyst Performance in NEEDA Generation

[0098] FIG. 2 is a bar graph of data using simulated recycle stream from Reactions 4 to 6 and Reactions 10 to 12, wherein the NEEDA formed in product mixtures over Comparative Catalyst Example A and Catalyst Example 1 at the EA feed concentrations of 5,000 ppm (Reaction 4 and Reaction 10), 8,750 ppm (Reaction 5 and Reaction 11), and 12,500 ppm (Reaction 6 and Reaction 12) are used to evaluate performance. The rate of NEEDA formation is increased when EA reactant concentration goes up. NEEDA concentrations were nearly one order of magnitude lower than the NMEDA, from between 0.02 wt. % to 0.05 wt. %. The Catalyst Example 1 formed less NEEDA than the Comparative Catalyst Example A, from between 0.002 wt. % to 0.004 wt. % lower (absolute) NEEDA in the effluent.

[0099] It will be apparent to persons of ordinary skill in the art that various modifications and variations can be made without departing from the scope disclosed herein. Since modifications, combinations, sub combinations, and variations of the disclosed embodiments, which incorporate the spirit and substance disclosed herein, may occur to persons of ordinary skill in the art, the scope disclosed herein should be construed to include everything within the scope of the appended claims and their equivalents.

[0100] For the purposes of defining the present technology, the transitional phrase “consisting of’ may be introduced in the claims as a closed preamble term limiting the scope of the claims86261 -WO-PCT / DOW 86261 WO33 to the recited components or steps and any naturally occurring impurities. For the purposes of defining the present technology, the transitional phrase “consisting essentially of’ may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps as well as any non-recited elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter. The transitional phrases “consisting of’ and “consisting essentially of’ may be interpreted to be subsets of the open-ended transitional phrases, such as “comprising” and “including,” such that any use of an open ended phrase to introduce a recitation of a series of elements, components, materials, or steps should be interpreted to also disclose recitation of the series of elements, components, materials, or steps using the closed terms “consisting of’ and “consisting essentially of.” For example, the recitation of a composition “comprising” components A, B, and C should be interpreted as also disclosing a composition “consisting of’ components A, B, and C as well as a composition “consisting essentially of’ components A, B, and C. Any quantitative value expressed in the present application may be considered to include open-ended embodiments consistent with the transitional phrases “comprising” or “including” as well as closed or partially closed embodiments consistent with the transitional phrases “consisting of’ and “consisting essentially of.”

[0101] As used in the Specification and appended Claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly indicates otherwise. The verb “comprises” and its conjugated forms should be interpreted as referring to elements, components or steps in a non-exclusive manner. The referenced elements, components or steps may be present, utilized or combined with other elements, components or steps not expressly referenced.

[0102] It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. The subject matter disclosed herein has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily imply that the component or feature is essential to the particular embodiment or to any other embodiment. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

Claims

86261 -WO-PCT / DOW 86261 WO34CLAIMS1. A process for producing amines by reductive amination, the process comprising: introducing a feed stream to a reaction zone, the feed stream comprising an amino alcohol and a reducing agent, introducing a recycle stream to a reaction zone, the recycle stream comprising light alkylamines and ammonia, contacting the feed stream and the recycle stream with a catalyst in the reaction zone in the presence of hydrogen, and producing a product stream comprising ethylenediamines, wherein the catalyst comprises: a carrier component selected from the group consisting of alumina, silica, and combinations thereof; and an active component comprising a first metal, a second metal, and a third metal, wherein the first metal is selected from the group consisting of cobalt, nickel, and copper, the second metal selected from a group consisting of rhenium, ruthenium, chromium, zinc, sodium, calcium, magnesium, strontium, lithium, potassium, barium, cesium, lanthanum, tungsten, iron, silver, titanium, manganese, aluminum, rhodium, platinum, palladium, iridium, and combinations thereof, and the third metal is niobium.2 The process of claim 1, wherein the product stream comprises from 450 ppm to 13000 ppm EEDA in EDA.3 The process of claim 1, wherein the product stream comprises from 450 ppm to 13000 ppm MEDA in EDA.4 The process of claim 1, wherein the light alkylamine comprises methylamine, ethylamine, and / or combinations thereof.5 The process of claim 1, wherein the amino alcohol is monoethanolamine.6 The process of any one of claims 1 to 5, wherein the reducing agent is ammonia.86261 -WO-PCT / DOW 86261 WO357. The process of any one of claims 1 to 6, wherein a mole ratio of reducing agent to amino alcohol is from 1 :1 to 30:1.

8. The process of any one of claims 1 to 7, wherein the process takes place at a pressure from 500 psi to 4000 psi, a temperature from 120 °C to 300 °C, and the amine feed stream has a space velocity from 0.5 hr'1to 13 hr'1.9 The process of any one of claims 1 to 8, wherein the feed stream comprises water, and the mass of water is less than or equal to 20 wt. % of the mass of amino alcohol in the feed stream.10 The process of any one of claims 1 to 9, wherein the hydrogen is supplied to the reaction zone as a separate stream.11 The process of any one of claims 1 to 10, wherein the hydrogen is supplied to the reaction zone as a component of the feed stream.12 The process of any one of claims 1 to 11, wherein a hydrogen concentration in the reaction zone is from 0.0001 mol. % to 50 mol. % of the total feed.13 The process of any one of claims 1 to 12, wherein a mass of niobium is from 0.5 wt. % to 5 0 wt. % based on the weight of the total catalyst.14 The process of any one of claims 1 to 13, wherein a mass of rhenium is from 0.5 wt.% to 5.0 based on the total weight of the catalyst.15 The process of any one of claims 1 to 14, wherein a mass of nickel is from 2 wt.% to 30 based on the total weight of the catalyst.16 The process of any one of claims 1 to 14, wherein an atomic ratio of rhenium to niobium is from 0.5:1 to 10:1.17 The process of any one of claims 1 to 14, wherein an atomic ratio of nickel to niobium is from 1 :1 to 50:1.86261 -WO-PCT / DOW 86261 WO3618. The process of any one of claims 1 to 14, wherein an atomic ratio of nickel to rhenium is from 1 :1 to 50:1.19.

19. The process of any one of claims 1 to 18, wherein the first metal is nickel and the second metal is rhenium.

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