Process for producing amines by reductive amination applying adjustable hydrogen concentration

Abstract

A process for producing amines by reductive amination, the process includes introducing a feed stream, the feed stream comprising an amino alcohol and a reducing agent, and hydrogen in a reaction zone of a reactor, and contacting the feed stream with a catalyst in the reaction zone. A hydrogen flow rate into the reaction zone is adjusted, and a product stream comprising ethyleneamines is extracted. 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

86148-WO-PCT / DOW 86148 WO1PROCESS FOR PRODUCING AMINES BY REDUCTIVE AMINATION APPLYING ADJUSTABLE HYDROGEN CONCENTRATIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 718,946 filed November 11, 2024, the contents of which are incorporated in their entirety herein.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, making these products desirable for at least this reason. The reductive amination chemical process unavoidably produces polyalkylene polyamines, many of which comprise greater than or equal to four nitrogen atoms in their molecular structure, and these polyalkylene polyamines are considered as unwanted by-products. The composition of the effluent stream may be dependent upon a variety of factors, including at least: catalyst composition, catalyst shape, the reactant ratio, temperature, pressure, influent flow rate, and hydrogen flow rate and / or hydrogen concentration in the reaction zone. Conventional catalysts deactivate at ultra-low hydrogen flow rates and / or concentrations. A present challenge in this chemical process is increasing the selectivity of high-value ethyleneamines in the reductive amination process.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 hydrogen86148-WO-PCT / DOW 86148 WO2 in a reaction zone of a reactor, contacting the feed stream with a catalyst in the reaction zone, 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. The conventional catalysts used in this process often results in unwanted byproducts, or may result in uncontrolled ratios of ethylenediamine to piperazine at a constant amino alcohol flow and a constant reducing agent flow. There is a need for a catalyst that is capable of catalyzing reactions under ultra-low hydrogen concentration so that selectivity adjustments may be made by altering hydrogen concentration; hydrogen flow rate may be decreased to lower hydrogen concentration and hydrogen flow rate may be increased to raise hydrogen concentration. Conventional catalysts cannot catalyze reactions under a variety of hydrogen concentrations to influence the effluent to a desired selectivity of byproducts, such as polyalkylene polyamines. Though a wide variety of reductive amination catalysts are known in industry, the catalysts are commonly hydrogenation catalysts. Nickel is a common catalyst component used in reductive amination, and may result in the relatively low selectivity of EDA. 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. 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, hydrogen concentration, temperature, pressure, and flow velocity. To reduce the amount of low market value products and to increase the amount of high market value products in the effluent stream, a catalyst capable of minimizing unwanted amine products under a variety of conditions 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, 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, 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 metal86148-WO-PCT / DOW 86148 WO3 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 showing the EDA selectivity sensitivity of catalyst to hydrogen flow rates at a pressure of 1900 psi and MEA conversion of 40% for Comparative Reaction Example A and B, and Reaction Example 1 and 2;

[0009] FIG. 2 is a bar graph showing the PIP, DETA and AEEA selectivities of catalysts to hydrogen flow rate at a pressure of 1900 psi and MEA conversion of 40% for Comparative Reaction Example A and B, and Reaction Example 1 and 2;

[0010] FIG. 3 is a bar graph showing the EDA sensitivity of catalyst to hydrogen flow rates at a pressure of 2100 psi and MEA conversion of 40% for Comparative Reaction Example C and D, and Reaction Example 3 and 4;

[0011] FIG. 4 is a bar graph showing the PIP, DETA and AEEA selectivities of catalysts to hydrogen flow rate at a pressure of 2100 psi and MEA conversion of 40% for Comparative Reaction Example C and D, and Reaction Example 3 and 4;

[0012] FIG. 5 is a scatter plot graph of MEA Conversion versus Time-on-Stream for Comparative Reaction Example E and F, Reaction Example 5 and 6, under the same reaction temperature at 167.5 °C;86148-WO-PCT / DOW 86148 WO4

[0013] FIG. 6 is a scatter plot graph of MEA Conversion versus Average Temperature for Comparative Reaction Example E and F, Reaction Example 5 and 6, and repeating experiments for Reaction Example 5 and 6 at high and ultra-low hydrogen flow rates; and

[0014] FIG. 7 is a scatter plot graph of MEA Conversion versus Average Temperature for Comparative Reaction Example E and F, and Reaction Example 5 and 6 and 7 and 8 at high and ultra-low hydrogen flow rates at different metal loadings.DETAILED DESCRIPTION

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] As used in this disclosure, “ultra-low concentration” generally refers to concentrations of hydrogen less than 1.3 mol. %. For instance, in embodiments the hydrogen concentration in the reaction zone may be less than or equal to 1.30 mol. %, 1.25 mol. %, 1.20 mol. %, 1.15 mol. %, 1.10 mol. %, 1.05 mol. %, 1.00 mol. %, 0.95 mol. %, 0.90 mol. %, 0.85 mol. %, 0.80 mol. %, 0.75 mol. %, 0.70 mol. %, 0.65 mol. %, 0.60 mol. %, 0.55 mol. %, 0.50 mol. %, 0.45 mol. %, 0.40 mol. %, 0.35 mol. %, 0.30 mol. %, 0.25 mol. %, 0.20 mol. %, 0.15 mol. %, 0.10 mol. %, or less than or equal to 0.05 mol. % hydrogen.86148-WO-PCT / DOW 86148 WO5

[0020] As used in this disclosure, “ultra-low flow” generally refers to flow rates used to achieve ultra-low concentration at a given MEA conversion rate. For example, hydrogen flow 1.79 xlO'3kg / hr / kg-catalyst, 8 SLPH (Standard Liters Per Hour) hydrogen, 7 mL / min MEA, and 10 mL / min NH3 with a hydrogen concentration of 1.24 mol. %.

[0021] As used in this disclosure, “given MEA conversion rate” generally refers to an MEA conversion that may be controlled by amino alcohol flow rate and reducing agent flow rate. Hydrogen concentration may be used to change the selectivity at a given MEA conversion rate.

[0022] In embodiments of a process for producing amines by reductive amination, the given MEA conversion may comprise from 40 wt. % to 42 wt. %. For instance, MEA conversion may be from 40.0 wt. % to 42.0 wt. %, from 40.0 wt. % to 41.8 wt. %, from 40.0 wt. % to41.6 wt. %, from 40.0 wt. % to 41.4 wt. %, from 40.0 wt. % to 41.2 wt. %, from 40.0 wt. % to 41.0 wt. %, from 40.0 wt. % to 40.8 wt. %, from 40.0 wt. % to 40.6 wt. %, from 40.0 wt. % to 40.4 wt. %, from 40.0 wt. % to 40.2 wt. %, 40.2 wt. % to 42.0 wt. %, from 40.2 wt. % to 41.8 wt. %, from 40.2 wt. % to 41.6 wt. %, from 40.2 wt. % to 41.4 wt. %, from 40.2 wt. % to 41.2 wt. %, from 40.2 wt. % to 41.0 wt. %, from 40.2 wt. % to 40.8 wt. %, from 40.2 wt. % to 40.6 wt. %, from 40.2 wt. % to 40.4 wt. %, 40.4 wt. % to 42.0 wt. %, from 40.4 wt. % to 41.8 wt. %, from 40.4 wt. % to 41.6 wt. %, from 40.4 wt. % to 41.4 wt. %, from 40.4 wt. % to 41.2 wt. %, from 40.4 wt. % to 41.0 wt. %, from 40.4 wt. % to 40.8 wt. %, from 40.4 wt. % to 40.6 wt. %, 40.6 wt. % to 42.0 wt. %, from 40.6 wt. % to 41.8 wt. %, from 40.6 wt. % to 41.6 wt. %, from 40.6 wt. % to 41.4 wt. %, from 40.6 wt. % to 41.2 wt. %, from40.6 wt. % to 41.0 wt. %, from 40.6 wt. % to 40.8 wt. %, 40.8 wt. % to 42.0 wt. %, from 40.8 wt. % to 41.8 wt. %, from 40.8 wt. % to 41.6 wt. %, from 40.8 wt. % to 41.4 wt. %, from 40.8 wt. % to 41.2 wt. %, from 40.8 wt. % to 41.0 wt. %, 41.0 wt. % to 42.0 wt. %, from 41.0 wt. % to 41.8 wt. %, from 41.0 wt. % to 41.6 wt. %, from 41.0 wt. % to 41.4 wt. %, from 41.0 wt. % to 41.2 wt. %, 41.2 wt. % to 42.0 wt. %, from 41.2 wt. % to 41.8 wt. %, from 41.2 wt. % to 41.6 wt. %, from 41.2 wt. % to 41.4 wt. %, 41.4 wt. % to 42.0 wt. %, from 41.4 wt. % to 41.8 wt. %, from 41.4 wt. % to 41.6 wt. %, 41.6 wt. % to 42.0 wt. %, from 41.6 wt. % to 41.8 wt. %, 41.8 wt. % to 42.0 wt. %.

[0023] In embodiments, the catalyst may be used in a process for producing amines by reductive amination, wherein the process may comprise an overall conversion of MEA from 20 wt. % to 99 wt. %. For example, the overall conversion of MEA may be from 20 wt. % to86148-WO-PCT / DOW 86148 WO690 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. %.

[0024] As used in this disclosure, “unwanted byproducts” generally refers to heavy amines, alkylamines, light alkylamines, or combinations thereof. As used in this disclosure “heavy amines” generally refers to polyalkylene polyamines or polyalkylene polyamines with molecular structures containing greater than or equal to four nitrogen atoms. As used in this disclosure “alkylamines” may refer to methylamine (MA), ethylamine (EA), N- methylethylenediamine (NMEDA), N-ethylethylenediamine (NEEDA), or combinations thereof, where “light alkylamines” may specifically refer to methylamine (MA), ethylamine (EA), or combinations thereof. As used in this disclosure, “>N4” generally refers to a molecular structure comprising greater than or equal to four nitrogen atoms.

[0025] 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.

[0026] As used throughout this disclosure, “active component” may comprise one or more metals, one or more metal oxides, or combinations thereof.

[0027] 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.

[0028] 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.

[0029] As used in this disclosure, “polyalkylene polyamines” refer to molecular structures of polyalkylene polyamines comprising four or greater nitrogen atoms, and may include, but are not limited to, triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), nitrilotrisethylamine (NTEA), diaminoethylpiperazine (DiAEP), piperazinoethylethylenediamine (PEEDA), 4-aminoethyltriethylenetetramine86148-WO-PCT / DOW 86148 WO7(AETETA), aminoethylpiperazinoethylethylenediamine (AEPEEDA), and / or piperazineoethyldiethylenetriamine (PEDETA).

[0030] 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.

[0031] As used in this disclosure, “time-on-stream” (hr) may be defined as the amount of time conducting reductive amination chemistry in the unit of hours.

[0032] 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.

[0033] As used in this disclosure, “conversion” refers specifically to the conversion of MEA on a weight basis.

[0034] 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.

[0035] In embodiments of a process for producing amines by reductive amination, the process 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, and producing a product stream comprising ethyleneamines, wherein the catalyst comprises an alumina, silica, or alumina / silica carrier component and an active component that comprises a first metal, a second metal and a third metal, wherein the first metal is selected from a 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. Without being bound by any particular theory, including niobium with the first and second metals as disclosed above improves the activity and selectivity of the catalyst by increasing dispersion of the first metal compared with conventional catalysts that do not include niobium. In addition, niobium does86148-WO-PCT / DOW 86148 WO8 not significantly leach from the catalyst and may extend catalyst life compared to other conventional catalysts under reaction conditions.

[0036] In embodiments of a process for producing amines by reductive amination, the process comprises introducing a feed stream, the feed stream comprising an amino alcohol and a reducing agent, and hydrogen in a reaction zone of a reaction, contacting the feed stream with a catalyst in the reaction zone, and producing a product stream comprising ethyleneamines, wherein the amino alcohol is monoethanolamine.

[0037] In embodiments of a process for producing amines by reductive amination, the process 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 reaction, contacting the feed stream with a catalyst in the reaction zone, and producing a product stream comprising ethyleneamines, wherein the reducing agent is ammonia.

[0038] 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, 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.

[0039] 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,86148-WO-PCT / DOW 86148 WO9 from 1500 psi to 2500 psi, 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.

[0040] 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.

[0041] In embodiments, a catalyst may be used in a process for producing amines by reductive amination, wherein the process 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 the catalyst in the reaction zone, and producing a product stream comprising ethyleneamines, the feed stream further comprising water, and the mass of the 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.

[0042] 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.

[0043] 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.86148-WO-PCT / DOW 86148 WO10

[0044] 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 10 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 10 mol.%, from 0.0001 mol.% to 9 mol.%, from 0.0001 mol. % to 8 mol. %, from 0.0001 mol. % to 7 mol. %, from 0.0001 mol. % to 6 mol. %, from 0.0001 mol. % to 5 mol. %, from 0.0001 mol. % to 4 mol. %, from 0.0001 mol. % to 3 mol. %, from 0.0001 mol. % to 2 mol. %, from 0.0001 mol. % to 1 mol. %, from 0.0001 mol. % to 0.5 mol. %, from 0.0001 mol. % to 0.0009 mol. %, from 0.0001 mol. % to 0.0008 mol. %, from 0.0001 mol. % to 0.0007 mol. %, from 0.0001 mol. % to 0.0006 mol. %, from 0.0001 mol. % to 0.0005 mol. %, from 0.0001 mol. % to 0.0004 mol. %, from 0.0001 mol. % to 0.0003 mol. %, from 0.0001 mol. % to 0.0002 mol. %, from 0.0002 mol. % to 10 mol. %, from 0.0002 mol. % to 5 mol. %, from 0.0002 mol. % to 1 mol. %, from 0.0002 mol. % to 0.0009 mol. %, from 0.001 mol. % to 10 mol. %, from 0.001 mol. % to 5 mol. %, from 0.001 mol. % to 1 mol. %, from 0.01 mol. % to 10 mol. %, from 0.01 mol. % to 5 mol. %, from 0.01 mol. % to 1 mol. % , from 0.1 mol. % to 10 mol. %, from 0.1 mol. % to 9 mol. %, from 0.1 mol. % to 8 mol. %, from 0.1 mol. % to 7 mol. %, from 0.1 mol. % to 6 mol. %, from 0.1 mol. % to 5 mol. %, from 0.1 mol. % to 4 mol. %, from 0.1 mol. % to 3 mol. %, from 0.1 mol. % to 2 mol. %, from 0.1 mol. % to 1 mol. %, from 1 mol. % to 10 mol. %, from 1 mol. % to 9 mol. %, from 1 mol. % to 8 mol. %, from 1 mol. % to 7 mol. %, from 1 mol. % to 6 mol. %, from 1 mol. % to 5 mol. %, from 1 mol. % to 4 mol. %, from 1 mol. % to 3 mol. %, from 1 mol. % to 2 mol. %, from 5 mol. % to 10 mol. %, from 5 mol. % to 9 mol. %, from 5 mol. % to 8 mol. %, from 5 mol. % to 7 mol. %, or from 5 mol. % to 6 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.

[0045] 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' 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, from86148-WO-PCT / DOW 86148 WO111 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 and production of undesired products may increase.

[0046] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream and hydrogen, which may be included in the feed stream, to a catalyst in which one or more of the active components is impregnated into the carrier component.

[0047] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream and hydrogen, which may be included in the feed stream, to a catalyst in which the carrier component is alumina. In another embodiment, a process for producing amines by reductive amination may comprise contacting the feed stream and hydrogen, which may be included in the feed stream, to a catalyst in which the carrier component is silica. In yet another embodiment, a process for producing amines by reductive amination may comprise contacting the feed stream and hydrogen, which may be included in the feed stream, to a catalyst in which the carrier component may comprise a mixture of alumina and silica.

[0048] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed 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. % to86148-WO-PCT / DOW 86148 WO1290 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.

[0049] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed 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. % to30 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 or 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.

[0050] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed 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.

[0051] In embodiments a process for producing amines by reductive amination may comprise contacting the feed 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, in86148-WO-PCT / DOW 86148 WO13 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.

[0052] In embodiments a process for producing amines by reductive amination may comprise contacting the feed 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, 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, from 1 :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, from 1 :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 8:1,86148-WO-PCT / DOW 86148 WO14 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, from 2:1 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 to 32:1, 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, from 2:1 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 to 46:1, 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, from 3:1 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, from 4:1 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, from 5:1 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 30:186148-WO-PCT / DOW 86148 WO15 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.

[0053] In embodiments a process for producing amines by reductive amination may comprise contacting the feed 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 atomic 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, 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, from 1 :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, from 1 :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 to86148-WO-PCT / DOW 86148 WO1639:1, from 2:1 to 38:1, from 2:1 to 37:1, from 2:1 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 to 32:1, 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, from 2:1 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, from2:1 to 3:1, from 3:1 to 50:1, from 3:1 to 47:1, from 3:1 to 46:1, 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, from 3:1 to 35:1, from 3:1 to 34:1, from3:1 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, from 4:1 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, from 5:1 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 14:1 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 40:186148-WO-PCT / DOW 86148 WO17 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.

[0054] In embodiments a process for producing amines by reductive amination may comprise contacting the feed 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 atomic ratio of the second metal to the third metal, wherein the ratio is an atomic ratio of the metal elements, may be 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, from0.9:1 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 to7.3:1, 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, from0.9:1 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 to3.9:1, 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, from 1.6:1 to 9.2:1, from 1.6:1 to 8.9:1,86148-WO-PCT / DOW 86148 WO18 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, from86148-WO-PCT / DOW 86148 WO194.7:1 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, from 5.1 :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.

[0055] In one or more embodiments, the catalyst does not comprise boron.

[0056] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed 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,86148-WO-PCT / DOW 86148 WO2040 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 110 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.

[0057] 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.

[0058] 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.86148-WO-PCT / DOW 86148 WO21

[0059] 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.

[0060] 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 doped86148-WO-PCT / DOW 86148 WO22 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.

[0061] 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 an unpassivated catalyst. In embodiments, the unpassivated catalyst is cooled and passivated to result in a catalyst.

[0062] 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.

[0063] 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.

[0064] 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.86148-WO-PCT / DOW 86148 WO23

[0065] 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.

[0066] 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, 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.

[0067] 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.

[0068] In embodiments an aqueous solution is formed by dissolving ammonium niobate (V) oxalate hydrate in water.

[0069] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed 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 45086148-WO-PCT / DOW 86148 WO24 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.

[0070] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream and hydrogen, which may be included in the feed stream, to a catalyst having 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.

[0071] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed stream and hydrogen, which may be included in the feed stream, to a catalyst having an active component that comprises from 2 wt. % to 30 wt. % nickel, based on the total weight of the catalyst. For instance, in embodiments the catalyst may86148-WO-PCT / DOW 86148 WO25 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.

[0072] 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 4.0 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.

[0073] In embodiments, a process for producing amines by reductive amination may comprise contacting the feed 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 of86148-WO-PCT / DOW 86148 WO26 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.% to2.5 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. % 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.% to4.5 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 in selectivity to the desired ethyleneamines; however, if the mass of niobium is too low, the selectivity to the desired ethyleneamine may be low.

[0074] In embodiments of a process for producing amines by reductive amination, the process 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, and producing a product stream comprising ethyleneamines, where the ethyleneamines may comprise ethylenediamine and piperazine.

[0075] In embodiments of a process for producing amines by reductive amination, hydrogen is introduced into the reaction zone as a separate stream from the feed stream, which comprises amino alcohol and a reducing agent, and the concentration of the hydrogen being introduced into the reaction zone may be increased or decreased to adjust the concentration of hydrogen present in the reaction zone. In embodiments, the amination process promotes high selectivity to EDA. In other embodiments, the amination process promotes high selectivity to DETA. Without being bound by any particular theory, it is believed that the activity or selectivity preference for EDA or DETA is a result of the addition of promoters to86148-WO-PCT / DOW 86148 WO27 a hydrogenation / dehydrogenation catalyst (e.g. Ni, Co, Cu, etc.). However, once the catalyst is charged to the reactor, the ability to promote desired selectivity may be limited by the process conditions, for example: ammonia to MEA feed mole ratio, temperature, hydrogen concentration, and recycle of products. Selectivity of EDA may be increased with decreased hydrogen concentration, but ultra-low hydrogen concentration has previously risked deactivating the catalyst. This is because hydrogen is co-fed with the reactants to prevent a rapid decline in catalytic activity due to the formation of metal nitrides and carbides, which are inactive. Specially, the reductive amination catalyst should be reduced before starting the reaction, and then continuously fed hydrogen during the course of the reaction to keep the catalyst active and functioning. The concentration of hydrogen added to the feed or the reactor can determine the catalyst’s productivity and selectivity to certain products. At a minimum, the concentration of hydrogen in the reaction zone should be sufficient to maintain the activity of the catalyst for the reductive amination by preventing the formation of the aforementioned nitrides and carbides on the catalyst. At too low of a hydrogen concentration, the catalyst surface becomes depleted of bound hydrogen, and the catalyst activity is reduced as its composition is changed. Eventually the catalyst will become depleted of its bound hydrogen, and when that occurs, the reaction terminates. In the course of the reaction, this can cause the composition of the reaction product to change, and what is found in the reactor is a composite composition of saturated and unsaturated (non-reduced) products that changes over the course of the limited life of the catalysts. In embodiments disclosed and described herein, the catalyst was found to be surprisingly stable at ultra-low hydrogen concentration and these unprecedented ultra-low hydrogen concentrations may be used to influence the selectivity of the products. It should be understood that the hydrogen concentration into the reaction zone may be decreased to decrease the amount of hydrogen present in the reaction zone, and the hydrogen concentration into the reaction zone may be increased to increase the amount of hydrogen present in the reaction zone. The hydrogen concentration is controlled by the hydrogen flow rate into the reaction zone, the hydrogen flow rate may be controlled by any suitable mechanism.

[0076] In embodiments a lower hydrogen concentration may result in increased EDA in the product stream. For example, 8 SLPH for 400 g catalyst (1.79 xlO'3kg / hr / kg-catalyst) or ultra-low H? mol. % (for example, <1 mol. %), in the presence of the catalyst disclosed and86148-WO-PCT / DOW 86148 WO28 described, may show an increase of 4-6% (absolute) EDA selectivity at comparable reaction conditions and MEA conversions compared to commercial catalysts.

[0077] In embodiments of a process for producing amines by reductive amination where the product stream comprises ethylenediamine and piperazine as the ethyleneamines, the flow rate of hydrogen into the reaction zone may be decreased to increase the ratio of ethylenediamine to piperazine at comparable MEA conversions.

[0078] In embodiments of a process for producing amines by reductive amination, the hydrogen flow may be increased to be greater than or equal to 1.8x 10'3kg / hr / kg-catalyst. For instance, in embodiments the hydrogen flow may be increased to be greater than or equal to 1.9x 10'3kg / hr / kg-catalyst, 2. Ox 10'3kg / hr / kg-catalyst, 2.5x 10'3kg / hr / kg-catalyst, 3. Ox 10'3kg / hr / kg-catalyst, 3.5x 10'3kg / hr / kg-catalyst, 4. Ox 10'3kg / hr / kg-catalyst, 4.5x 10'3kg / hr / kg-catalyst, 5. Ox 10'3kg / hr / kg-catalyst, 5.5x 10'3kg / hr / kg-catalyst, 6. Ox 10'3kg / hr / kg- catalyst, 6.5x 10'3kg / hr / kg-catalyst, 7. Ox 10'3kg / hr / kg-catalyst, 7.5x 10'3kg / hr / kg-catalyst, 8. Ox 10'3kg / hr / kg-catalyst, 8.5x 10'3kg / hr / kg-catalyst, 9. Ox 10'3kg / hr / kg-catalyst, 9.5x 10'3kg / hr / kg-catalyst, l.Ox 10'2kg / hr / kg-catalyst, l.lx 10'2kg / hr / kg-catalyst, 1.2x 10'2kg / hr / kg- catalyst, 1.3x 10'2kg / hr / kg-catalyst, 1.4x 10'2kg / hr / kg-catalyst, 1.5x 10'2kg / hr / kg-catalyst, 1.6x 10'2kg / hr / kg-catalyst, 1.7x 10'2kg / hr / kg-catalyst, 1.8x 10'2kg / hr / kg-catalyst, 1.9x 10'2kg / hr / kg-catalyst, 2. Ox 10'2kg / hr / kg-catalyst, 2.5x 10'2kg / hr / kg-catalyst, or 3. Ox 10'2kg / hr / kg-catalyst. The flow rate of hydrogen into the reaction zone may be increased such that the amount of hydrogen in the reaction zone is greater than or equal to 4.5 mol. %. For instance, in embodiments the hydrogen flow may be increased so that the amount of hydrogen in the reaction zone is greater than or equal to 5.0 mol. %, 5.5 mol. %, 6.0 mol. %, or 6.5 mol. %.

[0079] In embodiments of a process for producing amines by reductive amination, the hydrogen flow may be decreased to be less than or equal to 3. Ox 10'2kg / hr / kg-catalyst. For instance, in embodiments the hydrogen flow may be decreased to be less than or equal to 3. Ox 10'2kg / hr / kg-catalyst, 2.5x 10'2kg / hr / kg-catalyst, 2. Ox 10'2kg / hr / kg-catalyst, 1.9x 10'2kg / hr / kg-catalyst, 1.8x 10'2kg / hr / kg-catalyst, 1.7x 10'2kg / hr / kg-catalyst, 1.6x 10'2kg / hr / kg- catalyst, 1.5x 10'2kg / hr / kg-catalyst, 1.4x 10'2kg / hr / kg-catalyst, 1.3x 10'2kg / hr / kg-catalyst, 1.2x 10'2kg / hr / kg-catalyst, l.lx 10'2kg / hr / kg-catalyst, l.Ox 10'2kg / hr / kg-catalyst, 9.5x 10'3kg / hr / kg-catalyst, 9. Ox 10'3kg / hr / kg-catalyst, 8.5x 10'3kg / hr / kg-catalyst, 8. Ox 10'3kg / hr / kg- catalyst, 7.5x 10'3kg / hr / kg-catalyst, 7. Ox 10'3kg / hr / kg-catalyst, 6.5x 10'3kg / hr / kg-catalyst,86148-WO-PCT / DOW 86148 WO296. Ox 10'3kg / hr / kg-catalyst, 5.5x 10'3kg / hr / kg- catalyst, 5. Ox 10'3kg / hr / kg-catalyst, 4.5x 10'3kg / hr / kg-catalyst, 4. Ox 10'3kg / hr / kg-catalyst, 3.5x 10'3kg / hr / kg-catalyst, 3. Ox 10'3kg / hr / kg- catalyst, 2.5x 10'3kg / hr / kg-catalyst, 2. Ox 10'3kg / hr / kg-catalyst, 1.9x 10'3kg / hr / kg-catalyst, 1.8x 10'3kg / hr / kg-catalyst, 1.7x 10'3kg / hr / kg-catalyst, 1.6x 10'3kg / hr / kg-catalyst, 1.5x 10'3kg / hr / kg-catalyst, 1.4x 10'3kg / hr / kg-catalyst, 1.3x 10'3kg / hr / kg-catalyst, 1.2x 10'3kg / hr / kg- catalyst, l.lx 10'3kg / hr / kg-catalyst, or less than or equal to l.Ox 10'3kg / hr / kg-catalyst. The flow rate of hydrogen into the reaction zone may be decreased such that the amount of hydrogen in the reaction zone is less than or equal to 1.1 mol. %. For instance, in embodiments the hydrogen flow may be decreased so that the amount of hydrogen in the reaction zone is less than or equal to 1.0 mol. %, 0.9 mol. %, 0.8 mol. %, or 0.7 mol. %.

[0080] In embodiments of a process for producing amines by reductive amination, hydrogen concentration in the reaction zone may be ultra-low at a molar concentration less than or equal to 1.3 mol. %. For instance, in embodiments the hydrogen concentration in the reaction zone may be less than or equal to 1.30 mol. %, 1.25 mol. %, 1.20 mol. %, 1.15 mol. %, 1.10 mol. %, 1.05 mol. %, 1.00 mol. %, 0.95 mol. %, 0.90 mol. %, 0.85 mol. %, 0.80 mol. %, 0.75 mol. %, 0.70 mol. %, 0.65 mol. %, 0.60 mol. %, 0.55 mol. %, 0.50 mol. %, 0.45 mol. %, 0.40 mol. %, 0.35 mol. %, 0.30 mol. %, 0.25 mol. %, 0.20 mol. %, 0.15 mol. %, 0.10 mol. %, or less than or equal to 0.05 mol. % hydrogen.

[0081] 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 15 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 2086148-WO-PCT / DOW 86148 WO30 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.

[0082] 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%.

[0083] By controlling the hydrogen flow rate into the reaction zone, and thereby adjusting the hydrogen concentration within the reaction zone, the selectivity of the catalyst may be altered, thereby modifying the type and amount of target products and byproducts produced during the amination process. If the amount of hydrogen in the reaction zone is too high operation cost may increase, operation safety may decrease, and selectivity of desired products may be lowered; however, if the amount of hydrogen in the reaction zone is too low, the catalyst activity may be lost. As noted above, the amount of hydrogen in the reaction zone may be controlled by modifying the flow rate of hydrogen or concentration of hydrogen into86148-WO-PCT / DOW 86148 WO31 the reaction zone at unprecedented, ultra-low concentrations. In embodiments, this may be automated by measuring the amount of hydrogen in the reaction zone and increasing, via suitable automated mechanisms, the hydrogen flow rate into the reaction zone when the amount of hydrogen in the reaction zone reaches a predetermined low threshold, and likewise decreasing via suitable automated mechanisms, the hydrogen flow rate into the reaction zone when the amount of hydrogen in the reaction zone reaches a predetermined high threshold. The predetermined low threshold and the predetermined high threshold may be determined before the amination process begins by theoretical or experimental investigation and may be thresholds of the amount of hydrogen that correspond to desired selectivity of the catalyst for the amination process.

[0084] In embodiments of a process for producing amines by reductive amination, the process 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, and producing a product stream comprising ethyleneamines, wherein the amino alcohol is monoethanolamine.

[0085] 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 polyalkylene polyamines compared to methods using conventional catalysts.EXAMPLES

[0086] 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

[0087] 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 COMPONENT86148-WO-PCT / DOW 86148 WO32

[0088] 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

[0089] 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

[0090] 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 hydrate (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.

[0091] 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 1 hour, resulting in a first doped carrier.Second Impregnation and Second Calcining

[0092] 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 the86148-WO-PCT / DOW 86148 WO33 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.

[0093] 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

[0094] 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

[0095] 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.Passivation

[0096] 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.

[0097] 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.

[0098] 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. The86148-WO-PCT / DOW 86148 WO34Catalyst Example 1 surface area is 110 m2 / g. Catalyst Example 1 is a solid particle extrudate of 1 / 8” diameter.Catalyst Example 2 Preparation

[0099] Catalyst Example 2 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 2 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

[0100] The preparation of a carrier composite of this example is carried out in a manner described in patent EP 0737669 Al, 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

[0101] The active component of Catalyst Example 2 comprises a first metal of the active component that is nickel. The second metal of the active component in Catalyst Example 2 is rhenium. The third metal of the active component in Catalyst Example 2 is niobium. In order 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 2.First Impregnation and First Calcining

[0102] 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 7.54 g ammonium niobate (V) oxalate hydrate (product number 525839 from MilliporeSigma) in deionized water in a first vessel. A second vessel was charged with 146.19 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 impregnation carrier.86148-WO-PCT / DOW 86148 WO35

[0103] To remove residual impurities or volatile substances and promote thermal decomposition of the niobium salt from the first impregnation carrier, the first impregnation carrier was calcined in air at 340 °C for 1 hour, resulting in a first doped carrier.Second Impregnation and Second Calcining

[0104] 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 86.68 g nickel nitrate hexahydrate (product number 203874 from MilliporeSigma) and dissolving 6.15 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 with the first doped carrier to create a second impregnation carrier.

[0105] 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 1 hour, resulting in a second doped carrier.Reduction

[0106] 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 2 catalyst.Cooling

[0107] The unpassivated Experiment 2 catalyst was cooled to below 100°C in hydrogen. After cooling to below 100 °C, the catalyst was further cooled under nitrogen.Passivation

[0108] 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 2 catalyst was passivated by exposing the catalyst to a mixture of oxygen and nitrogen at room temperature. Approximately 180 seem (standard cubic86148-WO-PCT / DOW 86148 WO36 centimeters) of 5% O2 / N2 and 420 seem of N2 are introduced to the catalyst until the catalyst reaches room temperature.

[0109] 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.

[0110] Catalyst Example 2 carrier component is 80 wt. % alumina and 20 wt. % silica. Catalyst Example 2 active components mass to the total catalyst weight (carrier component and active component) is 10.30 wt. % nickel, 2.51 wt. % rhenium, and 1.36 wt. % niobium. Catalyst Example 2 is a solid particle extrudates of 1 / 8” diameter. Catalyst Example 2 has a greater metal loading of niobium compared to Catalyst Example 1.Comparative Catalyst Example A Preparation

[0111] 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.

[0112] 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

[0113] Reaction Examples 1 to 8 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 in 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.[L0114 10086148-WO-PCT / DOW 86148 WO37

[0115] 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 f eed-wt% of MEA in the product

[0116] MEA Conversion = x 100 wt% of MEA in the feedReaction Conditions

[0117] 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.

[0118] 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). 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. 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. The reaction conditions and catalysts used for Reaction Examples and Comparative Reaction Examples are summarized in detail in Table 1.

[0119] Table 1. Summary of the reactor conditions at Reaction Examples 1 to 8 and Comparative Reaction Examples A to F.86148-WO-PCT / DOW 86148 WO38Results - Selectivity using Catalyst Example 1 and Comparative Catalyst Example A

[0120] As demonstrated in the tabulated data of Table 2 and Table 3 and their corresponding charts in FIG. 1 to FIG. 4, the selectivity differences (“delta”) for hydrogen flow rate changes, resulting in hydrogen concentration changes at an unchanged MEA feed rate, is a greater delta for Catalyst Example 1 (comparing Reaction Example 1 and 2, or 3 and 4) than for hydrogen concentration changes for Comparative Catalyst Example A (comparing Comparative Reaction Examples A and B or C and D). These results demonstrate a greater flexibility and sensitivity of the Catalyst Example 1 compared to Comparative Catalyst Example A.86148-WO-PCT / DOW 86148 WO39

[0121] Table 2. Comparative Catalyst Example A delta results and Catalyst Example 1 delta results at 1900 psig, 10.3 mL / min MEA Flow, 1.56 hr'1MEA SV, and 17.1 mL / min NEI3.

[0122] Table 3. Comparative Catalyst Example A delta results and Catalyst Example 1 delta results at 2100 psig, 10.3 mL / min MEA Flow, 1.56 hr'1MEA SV, and 17.1 mL / min NH3.Results - Selectivity using Catalyst Example 1, Catalyst Example 2, and Comparative Catalyst Example A

[0123] Comparative Catalyst Example A was unstable at ultra-low hydrogen concentration conditions (8 SLPH or 1.79 x 10-3 kg / hr / kg-catalyst), while Catalyst Example 1 was stable under the same conditions. FIG. 5 shows the time-on-stream catalyst activity (MEA conversions) of Comparative Reaction Example E and F, as well as Reaction Example 5 and 6, under the sample reactor temperature at 167.5 °C with a variation of ± 0.5 °C. The results show that the Comparative Catalyst Example A gave a reasonable MEA conversion at 25 SLPH (5.59 x 10'3kg / hr / kg-catalyst) hydrogen flow (Comparative Reaction Example E), but a decrease of activity was observed when hydrogen flow was lowered to 8 SLPH86148-WO-PCT / DOW 86148 WO40(Comparative Reaction Example F). The Catalyst Example 1, on the contrary, remained at similar MEA conversions under both 25 SLPH (Reaction Example 5) and 8 SLPH (Reaction Example 6) hydrogen flow.

[0124] FIG. 6 shows the MEA conversions as a function of reaction temperature for Comparative Catalyst Example A and Catalyst Example 1 under both high (25 SLPH, Comparative Reaction Example E and Reaction Example 5) and low (8 SLPH, Comparative Reaction Example F and Reaction Example 6) hydrogen flows.). The MEA conversion rate of the ultra-low hydrogen concentration conditions with Comparative Catalyst Example A is lower than the results shown in FIG. 6 at 25 SLPH, due to the loss of activity lacking in hydrogen, while Catalyst Example 1 exhibited stable performance at high hydrogen concentration (Reaction Example 5) and ultra-low hydrogen concentration (Reaction Example 6).

[0125] Catalyst Example 2 increases the metal loading of niobium, and is used for high and ultra-low hydrogen concentration reactions.

[0126] FIG. 7 shows Catalyst Example 1 with a metal loading of Ni / Re / Nb at 8.2 / 2.1 / 1.1 and Catalyst Example 2 with a metal loading of Ni / Re / Nb at 10.3 / 2.51 / 1.36, respectively, as compared to Comparative Catalyst Example A performance without niobium metal loading, and at reactions of high hydrogen concentration (Reaction Example 7) and ultra-low hydrogen concentration (Reaction Example 8).

[0127] Data shows the niobium promoted catalyst maintains catalytic activity at ultra-low hydrogen concentrations compared to catalysts that are not promoted with niobium.

[0128] 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.

[0129] 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 claims 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 recited86148-WO-PCT / DOW 86148 WO41 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.”

[0130] 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.

[0131] 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

86148-WO-PCT / DOW 86148 WO42CLAIMS1. A process for producing amines by reductive amination, the process comprising: 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, adjusting a hydrogen flow rate into the reaction zone, 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.

2. The process of claim 1, wherein the product stream comprises ethylenediamine and piperazine, and the hydrogen flow is increased to decrease the ratio of ethylenediamine to piperazine at a constant amino alcohol flow and a constant reducing agent flow.

3. The process of claim 2, where the hydrogen flow rate is increased to at least 1.1 x 10"2kg / hr / kg-catalyst.

4. The process of claim 1, wherein the product stream comprises ethylenediamine and piperazine, and86148-WO-PCT / DOW 86148 WO43 the hydrogen flow is decreased to increase the ratio of ethylenediamine to piperazine at a constant amino alcohol flow and a constant reducing agent flow.

5. The process of claim 4, where the hydrogen flow rate is decreased to at least 1.79 x 1 O'3kg / hr / kg-catalyst.

6. The process of any one of claims 1 to 5, wherein the amino alcohol is monoethanolamine.

7. The process of any one of claims 1 to 6, wherein the reducing agent is ammonia.

8. The process of any one of claims 1 to 7, wherein the mole ratio of reducing agent to amino alcohol is from 1 :1 to 30:1.

9. The process of any one of claims 1 to 8, wherein the process takes place at a pressure from 500 psi to 4000 psi.

10. The process of any one of claims 1 to 9, wherein the process takes place at a temperature from 120 °C to 300 °C.

11. The process of any one of claims 1 to 10, wherein the feed stream comprises water, and the mass of water is up to 50 wt. % of the mass of amino alcohol in the feed stream.

12. The process of any one of claims 1 to 11, wherein the hydrogen gas is supplied to the reactor as a separate feed stream.

13. The process of any one of claims 1 to 12, wherein the amine feed stream has a space velocity greater than or equal to 0.5 hr'1.

14. The process of any one of claims 1 to 13, wherein the first metal is nickel and the second metal is rhenium, the first and second metal are supported on a carrier comprising 586148-WO-PCT / DOW 86148 WO44 wt. % to 65 wt. % silica and further comprises a carrier surface area of from 30 m2 / g to 450 m2 / g.

15. The process of any one of claims 1 to 14, wherein a mass of niobium is from 0.5 wt. % to 5.0 wt. % based on the total weight of the catalyst.

16. The process of any one of claims 1 to 15, wherein the total rhenium content in the total catalyst is from 0.5 wt.% to 5.0 wt.% based on the total weight of the catalyst.

17. The process of any one of claims 1 to 16, wherein a mass of nickel is from 2 wt.% to 30 wt.% based on the total weight of the catalyst.

18. The process of any one of claims 1 to 17, wherein an atomic ratio of rhenium to niobium is from 0.5:1 to 10:1.

19. The process of any one of claims 1 to 17, wherein an atomic ratio of nickel to niobium is from 1 :1 to 50:1.

20. The process of any one of claims 1 to 17, wherein an atomic ratio of nickel to rhenium is from 1 :1 to 50:1.

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