Catalyst, preparation method and method for preparing triethylamine through hydroamination of coal-based ethanol

Abstract

The invention discloses a catalyst, a preparation method and a method for preparing triethylamine through hydroamination of coal-based ethanol. The catalyst comprises a carrier and an active component loaded on the carrier, the active component comprises an active element; the active elements are cobalt and rhenium; the carrier is rod-like aluminum oxide; and the length-diameter ratio of the rod-like aluminum oxide is 5-30. Compared with a CoRe / Al2O3 (irregular morphology) catalyst, the selectivity of triethylamine in the catalyst prepared by the method disclosed by the invention can be obviously improved.

Description

Technical Field

[0001] The present application relates to a catalyst and a preparation method thereof, as well as a method for preparing triethylamine by hydroamination of coal-based ethanol, and belongs to the technical field of chemical catalyst preparation. Background Art

[0002] Ethylamine is a derivative formed by replacing the hydrogen atom of an ammonia molecule with an ethyl group. It mainly includes monoethylamine, diethylamine, triethylamine, etc. It is an important fine chemical intermediate that can react with a variety of compounds to form derivatives. It is widely used in industries such as medicine, pesticides, chemical additives, military industry and new energy.

[0003] With the continuous increase in my country's lithium battery production capacity in recent years, demand for triethylamine-related products, such as vinylene carbonate and the novel lithium salt LiFSi, has surged. Consequently, market demand for triethylamine has surged. Market research indicates that demand for triethylamine is expected to increase from 72,100 tons to 103,100 tons between 2022 and 2025.

[0004] Currently, ethylamine is mainly obtained globally through the hydroamination of bioethanol. However, my country's bioethanol production is limited and expensive. The successful development and industrial production of lower-priced coal-based ethanol (>3 million tons / year) provides raw material guarantees and price advantages for the implementation of this project.

[0005] Using ethanol and liquid ammonia as raw materials, a pressure reaction in the presence of hydrogen produces an ethylamine mixture, which is then separated to produce the ethylamine product. This process offers advantages such as no side effects, high product quality, low energy consumption, and the ability to simultaneously produce monoethylamine, diethylamine, and triethylamine. Currently, cobalt- and / or nickel-based catalysts used in the hydroamination of ethanol to produce ethylamines are typically supported by irregularly shaped alumina and / or silica.

[0006] US Patent No. 2363721 provides a nickel-irregular alumina catalyst, but its activity in the ethanol amination reaction is relatively low. Chinese Patent No. CN1436596A provides a low-grade fatty amine catalyst, which is supported by a carrier with active components such as cobalt and calcium, wherein the active components account for 10-50% of the catalyst weight. The catalyst preparation process is complex and the selectivity is not ideal. Chinese Patent No. CN101869836A provides a low-grade fatty amine catalyst, a preparation method and its application, which uses irregular alumina as a carrier and the active components include: (1) Co, 10-50%; (2) at least one of Ce, Nd, Pr and Gd, 0.01-5%; (3) at least one of Cr, Ba, Ag, Mn, Ti, Ge and Zr, 0.01-10%. The catalyst shows good ethanol amination reaction performance at a higher reaction temperature (170°C), but the low-temperature activity and stability need to be improved, and it is not conducive to the selectivity of ethylamine.

[0007] Chinese patent CN112044447A provides a catalyst, preparation method, and application for synthesizing monoethylamine. The catalyst comprises irregularly shaped alumina particles and cobalt, palladium, and rhenium deposited on the surface of the alumina particles. When ethanol is hydroamination to produce monoethylamine, the monoethylamine selectivity is greater than or equal to 86% (ethanol conversion is greater than or equal to 61%, and ethylamine selectivity is greater than or equal to 99.9%).

[0008] Chinese patent CN201911009864.9 discloses a catalyst for preparing ethylamine by hydroamination of ethanol, as well as its preparation method and application. The catalyst contains 5-25% Ni, 0.5-30% Sn and 55-94.5% of a carrier (at least one of irregular morphology alumina, silica, zirconia and titania). The selectivities of the products monoethylamine, diethylamine and triethylamine are: ~18%, ~54% and ~28%, respectively.

[0009] In the reaction of hydroamination of coal-based ethanol to produce triethylamine, impurities such as ester compounds, polymers, and pyridine bases in the coal-based ethanol affect the reaction performance of the catalyst (as shown in Table 1). There are no reports in the literature or patents on how to develop a catalyst for the hydroamination of coal-based ethanol to produce triethylamine that is resistant to impurities, low in temperature, highly active, and has high triethylamine selectivity. Summary of the Invention

[0010] According to one aspect of the present application, a catalyst is provided, comprising a carrier and an active component supported on the carrier;

[0011] The active component includes an active element;

[0012] The active elements are cobalt and rhenium;

[0013] The carrier is rod-shaped alumina;

[0014] The aspect ratio of the rod-shaped alumina is 5-30.

[0015] Optionally, the aspect ratio of the rod-shaped alumina is independently selected from any value among 5, 10, 15, 20, 25, 30, or a range between any two of the above points.

[0016] Optionally, the aspect ratio of the rod-shaped alumina is 10-20.

[0017] Optionally, the mass of the cobalt is 10-30 wt.% of the mass of the catalyst, the mass of the rhenium is 0.1-0.5 wt.% of the mass of the catalyst, and the masses of the cobalt and rhenium are calculated as the masses of the cobalt and rhenium elements.

[0018] Optionally, the mass of the cobalt is any value independently selected from 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 28 wt.%, 30 wt.% or a range between any two of the above values ​​based on the mass of the catalyst.

[0019] Optionally, the mass of the rhenium is any value independently selected from 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.% or a range between any two of the above values ​​based on the mass of the catalyst.

[0020] According to another aspect of the present application, a method for preparing the catalyst described above is provided, the method comprising:

[0021] In a closed reactor, the carrier is impregnated with a mixture containing a cobalt precursor and a rhenium precursor, and then dried, calcined, and reduced to obtain the catalyst;

[0022] The carrier is prepared by mixing and kneading rod-shaped aluminum oxide powder.

[0023] Optionally, the cobalt precursor is cobalt nitrate.

[0024] Optionally, the rhenium precursor is ammonium rhenate.

[0025] Optionally, the mixture further comprises a solvent, and the solvent is water.

[0026] Optionally, the impregnation is an equal volume closed impregnation.

[0027] Optionally, the immersion temperature is 60-90° C., and the immersion time is 2-5 hours.

[0028] Optionally, the immersion temperature is independently selected from any value of 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C or a range between any two of the above values.

[0029] Optionally, the immersion time is independently selected from any value among 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or a range between any two of the above values.

[0030] Optionally, the drying temperature is 110-120° C., and the drying time is 6-12 hours.

[0031] Optionally, the drying temperature is independently selected from any value among 110°C, 112°C, 115°C, 118°C, 120°C, or a range between any two of the above values.

[0032] Optionally, the drying time is independently selected from any value among 6h, 7h, 8h, 9h, 10h, 11h, 12h or a range between any two of the above.

[0033] Optionally, the calcination atmosphere is an inert atmosphere.

[0034] Optionally, the inert atmosphere is selected from at least one of nitrogen, argon and helium.

[0035] Optionally, the calcination temperature is 350-500° C., and the calcination time is 2-5 hours.

[0036] Optionally, the calcination temperature is independently selected from any value among 350°C, 400°C, 450°C, 500°C, or a range between any two of the above values.

[0037] Optionally, the calcination time is independently selected from any value among 2h, 3h, 4h, 5h or a range between any two of the above.

[0038] Optionally, the reducing atmosphere is hydrogen.

[0039] Optionally, the reduction temperature is 350-500° C., and the reduction time is 10-30 h.

[0040] Optionally, the reduction temperature is independently selected from any value among 350°C, 400°C, 450°C, 500°C or a range between any two of the above values.

[0041] Optionally, the reduction time is independently selected from any value of 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, or a range between any two of the above.

[0042] According to another aspect of the present application, a method for preparing triethylamine by hydroamination of coal-based ethanol is provided, the method comprising:

[0043] The raw materials containing coal-based ethanol, hydrogen, ammonia and diethylamine are contacted with a catalyst to react to obtain a product containing ethylamine;

[0044] The catalyst is selected from the catalysts described above.

[0045] Optionally, the molar ratio of the coal-based ethanol to the ammonia is 2 to 6:1.

[0046] Optionally, the molar ratio of the coal-based ethanol to the ammonia is independently selected from any value of 2:1, 3:1, 4:1, 5:1, 6:1 or a range between any two of the above values.

[0047] Optionally, the molar ratio of the coal-based ethanol to the diethylamine is 3 to 6:1.

[0048] Optionally, the molar ratio of the coal-based ethanol to the diethylamine is independently selected from any value of 3:1, 4:1, 5:1, 6:1 or a range between any two of the above.

[0049] Optionally, the molar ratio of the hydrogen to the coal-based ethanol is 1 to 5:1.

[0050] Optionally, the weight space velocity of the coal-based ethanol is 0.08 to 0.3 h -1 .

[0051] Optionally, the weight space velocity of the coal-based ethanol is independently selected from 0.08h -1 , 0.10h -1 , 0.125h -1 , 0.15h -1 , 0.175h -1 , 0.2h -1 , 0.25h -1 , 0.3h -1 Any value in or a range of values ​​between any two of the above.

[0052] Optionally, the reaction pressure is 0.8-2.0 MPa.

[0053] Optionally, the reaction pressure is independently selected from any value among 0.8 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa or a range between any two of the above values.

[0054] Optionally, the reaction temperature is 120-200°C.

[0055] Optionally, the reaction temperature is independently selected from any value of 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C or a range between any two of the above values.

[0056] As an optional implementation method, the present application is implemented through the following technical solutions:

[0057] The preparation method of the catalyst comprises: sealingly immersing the carrier in a solution containing cobalt and rhenium precursors at a certain temperature, and then drying, calcining in an inert atmosphere, and reducing to obtain the catalyst.

[0058] The cobalt precursor is cobalt nitrate; the rhenium precursor is ammonium rhenate.

[0059] The carrier is prepared by mixing and kneading rod-shaped alumina powder.

[0060] Optionally, the catalyst preparation method is: mixing and kneading rod-shaped alumina powder to obtain an Al2O3 (rod-shaped) carrier, then sealingly impregnating equal volumes of cobalt nitrate and ammonium rhenate solutions at a certain temperature, and then drying, calcining and reducing under an inert atmosphere to obtain the required CoRe / Al2O3 (rod-shaped) catalyst.

[0061] In this application, the content of impurities such as trace ester compounds, polymers and pyridine base in "coal-based ethanol" is 0-8000ppm;

[0062] The support is rod-shaped alumina, marked as "R".

[0063] The beneficial effects of this application include:

[0064] The CoRe / Al2O3(R) catalyst prepared by the present invention fully utilizes the rod-shaped morphology to effectively improve the dispersion of active metals. In addition, the hydrogen overflow and isolation effect of Re, as well as the calcination in an inert atmosphere, can inhibit the aggregation of cobalt oxide. After hydrogen reduction, the reduced cobalt and rhenium are more evenly distributed in the rod-shaped alumina, and are less likely to agglomerate during the reaction process, which is beneficial to the diffusion of reactants and products in the catalyst and the improvement of the reaction activity of the catalyst. When used for ethanol amination to ethylamine, the selectivity of triethylamine can be significantly improved compared with the CoRe / Al2O3 (irregular morphology) catalyst. DETAILED DESCRIPTION

[0065] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0066] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0067] The analysis method in the examples of this application is as follows:

[0068] The aspect ratio of rod-shaped alumina crystals was obtained by SEM (HITACHI SU1510).

[0069] The weight contents of cobalt and rhenium in the catalyst were determined by XRF (PANAlytical).

[0070] The raw materials and products were analyzed by gas chromatography Agilent 7890A.

[0071] In the examples of the present application, the catalyst activity evaluation indicators, namely, ethanol conversion rate, ammonia conversion rate and triethylamine selectivity, are calculated based on weight:

[0072] Ethanol conversion rate:

[0073]

[0074] Ammonia conversion rate:

[0075]

[0076] Triethylamine selectivity:

[0077]

[0078] In the above formula, m represents weight.

[0079] In the following examples, "A" in Al2O3(A) refers to an irregular morphology.

[0080] Comparative Example 1

[0081] A catalyst for the hydroamination of coal-based ethanol (containing impurities such as ester compounds, polymers, and pyridine bases at a content of ∼3000 ppm) to produce triethylamine, the catalyst being CoRe / Al2O3(A)-1. The catalyst comprises an active component and a carrier, wherein the active components are cobalt and rhenium, and the carrier is an Al2O3(A)-1 carrier. The cobalt content is 25 wt.%, and the rhenium content is 0.2 wt.%, based on the weight percentage of the catalyst.

[0082] The catalyst is prepared according to the following method:

[0083] (1) Preparation of Al2O3(A)-1 carrier: Irregular morphology alumina (specific surface area and pore volume are 224m 2 / g and 0.509cm 3 / g) and sesbania powder were mixed and kneaded in a weight ratio of 98:2, and then dried at 120°C and calcined at 500°C for 3h;

[0084] (2) Cobalt nitrate and ammonium rhenate were weighed according to the contents of the active component cobalt and the auxiliary agent rhenium, and the cobalt nitrate and ammonium rhenate were dissolved in water to obtain an impregnation solution. The Al2O3(A)-1 carrier was placed in the impregnation solution and impregnated in a closed manner at 70°C for 3 hours; dried at 120°C for 6 hours, and then calcined at 500°C in a nitrogen atmosphere for 2 hours, hydrogen was introduced, and reduced at 500°C for 10 hours to obtain a catalyst CoRe / Al2O3(A)-1 with cobalt and rhenium contents of 25wt% and 0.2wt%, respectively.

[0085] The performance of the catalyst CoRe / Al2O3(A)-1 in the hydroamination of coal-based ethanol to triethylamine was evaluated in a small-scale reactor. The reactor diameter was 9 mm, the catalyst loading was 8 g, and the temperature was raised to 140°C at a rate of 10°C / min under ammonia conditions. Coal-based ethanol was introduced for 100 hours. The reaction conditions were: temperature 140°C, pressure 1.5 MPa, and a coal-based ethanol weight space velocity of 0.2 h. -1 The molar ratio of coal-based ethanol to ammonia was 2:1, the molar ratio of coal-based ethanol to diethylamine was 6:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC. Detailed evaluation results are shown in Table 1. The reaction performance evaluation results for bioethanol, using the same catalyst and reaction conditions, are shown in Table 1 when coal-based ethanol was replaced with bioethanol.

[0086] Comparative Example 2

[0087] A catalyst for the hydroamination of coal-based ethanol (containing impurities such as ester compounds, polymers, and pyridines at a content of ∼3000 ppm) to produce triethylamine, comprising Co / Al2O3(R)-1, an active ingredient, and an Al2O3(R)-1 carrier; wherein the cobalt content is 25% by weight of the catalyst.

[0088] The catalyst is prepared according to the following method:

[0089] (1) Preparation of Al2O3(R)-1 carrier: rod-shaped alumina (specific surface area and pore volume are 228m 2 / g and 0.557cm 3 / g, the length / diameter ratio of the crystal is 10) and sesbania powder are mixed and kneaded in a weight ratio of 98:2, and then dried at 120°C and calcined at 500°C for 3h;

[0090] (2) According to the content of cobalt as the active component, cobalt nitrate was weighed and dissolved in water to obtain an impregnation solution. The Al2O3(R)-1 carrier was placed in the impregnation solution and impregnated in a sealed manner at 70°C for 3 hours; dried at 120°C for 6 hours, and then calcined at 500°C in a nitrogen atmosphere for 2 hours. Hydrogen was introduced and reduced at 500°C for 10 hours to obtain a catalyst Co / Al2O3(R)-1 with a cobalt content of 25 wt.%.

[0091] The performance of the Co / Al2O3(R)-1 catalyst in the hydroamination of coal-based ethanol to triethylamine was evaluated in a small-scale reactor. The reactor was 9 mm in diameter and loaded with 8 g of catalyst. The reactor was heated to 140°C at a rate of 10°C / min under ammonia conditions, and coal-based ethanol was introduced for 100 hours. The reaction conditions were: temperature 140°C, pressure 1.5 MPa, and a coal-based ethanol weight space velocity of 0.2 h / min. -1 The molar ratio of coal-based ethanol to ammonia was 2:1, the molar ratio of coal-based ethanol to diethylamine was 6:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC. The specific evaluation results are shown in Table 1.

[0092] Comparative Example 3

[0093] A catalyst for the hydroamination of coal-based ethanol (containing impurities such as ester compounds, polymers, and pyridine bases at a content of ∼3000 ppm) to produce triethylamine, comprising CoRe / Al2O3(R)-1, an active ingredient, and an Al2O3(R)-1 carrier. The active ingredients are cobalt and rhenium, and the carrier is an Al2O3(R)-1 carrier. The cobalt content is 25 wt.%, and the rhenium content is 0.2 wt.%, based on the weight percentage of the catalyst.

[0094] The catalyst is prepared according to the following method:

[0095] (1) Preparation of Al2O3(R)-1 carrier: rod-shaped alumina (specific surface area and pore volume are 228m 2 / g and 0.557cm 3 / g, the length / diameter ratio of the crystal is 10) and sesbania powder are mixed and kneaded in a weight ratio of 98:2, and then dried at 120°C and calcined at 500°C for 3h;

[0096] (2) Cobalt nitrate and ammonium rhenate were weighed according to the contents of the active components cobalt and rhenium, and the cobalt nitrate and ammonium rhenate were dissolved in water to obtain an impregnation solution. The Al2O3(R)-1 carrier was placed in the impregnation solution and impregnated in a closed manner at 70°C for 3 hours; dried at 120°C for 6 hours, and then calcined at 500°C in an air atmosphere for 2 hours. Hydrogen was introduced and reduced at 500°C for 10 hours to obtain a catalyst CoRe / Al2O3(R)-1air (air calcined) with a cobalt content of 25wt.%.

[0097] The performance of the catalyst CoRe / Al2O3(R)-1air in the hydroamination of coal-based ethanol to triethylamine was evaluated in a small-scale reactor. The reactor diameter was 9 mm, the catalyst loading was 8 g, and the temperature was raised to 140°C at a rate of 10°C / min under ammonia conditions. Coal-based ethanol was introduced for 100 hours. The reaction conditions were: temperature 140°C, pressure 1.5 MPa, and a coal-based ethanol weight space velocity of 0.2 h-1. -1 The molar ratio of coal-based ethanol to ammonia was 2:1, the molar ratio of coal-based ethanol to diethylamine was 6:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC. The specific evaluation results are shown in Table 1.

[0098] Example 1

[0099] A catalyst for the hydroamination of coal-based ethanol (containing impurities such as ester compounds, polymers, and pyridine bases at a content of ∼3000 ppm) to produce triethylamine, comprising CoRe / Al2O3(R)-1, an active ingredient, and an Al2O3(R)-1 carrier. The active ingredients are cobalt and rhenium, and the carrier is an Al2O3(R)-1 carrier. The cobalt content is 25 wt.%, and the rhenium content is 0.2 wt.%, based on the weight percentage of the catalyst.

[0100] The catalyst is prepared according to the following method:

[0101] (1) Preparation of Al2O3(R)-1 carrier: rod-shaped alumina (specific surface area and pore volume are 228m 2 / g and 0.557cm 3 / g, the length / diameter ratio of the crystal is 10) and sesbania powder are mixed and kneaded in a weight ratio of 98:2, and then dried at 120°C and calcined at 500°C for 3h;

[0102] (2) Cobalt nitrate and ammonium rhenate were weighed according to the contents of the active components cobalt and rhenium, and the cobalt nitrate and ammonium rhenate were dissolved in water to obtain an impregnation solution. The Al2O3(R)-1 carrier was placed in the impregnation solution and impregnated in a closed manner at 70°C for 3 hours; dried at 120°C for 6 hours, and then calcined at 500°C in a nitrogen atmosphere for 2 hours. Hydrogen was introduced and reduced at 500°C for 10 hours to obtain a catalyst CoRe / Al2O3(R)-1 with a cobalt content of 25wt.% and a rhenium content of 0.2wt.%.

[0103] The performance of the catalyst CoRe / Al2O3(R)-1 in the hydroamination of coal-based ethanol to triethylamine was evaluated in a small-scale reactor. The reactor was 9 mm in diameter and loaded with 8 g of catalyst. The reactor was heated to 140°C at a rate of 10°C / min under ammonia conditions, and coal-based ethanol was introduced for 100 hours. The reaction conditions were: temperature 140°C, pressure 1.5 MPa, and a coal-based ethanol weight space velocity of 0.2 h-1. -1 The molar ratio of coal-based ethanol to ammonia was 2:1, the molar ratio of coal-based ethanol to diethylamine was 6:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC. Detailed evaluation results are shown in Table 1. The reaction performance evaluation results for bioethanol, using the same catalyst and reaction conditions, are shown in Table 1 when coal-based ethanol was replaced with bioethanol.

[0104] Example 2

[0105] A catalyst for the hydroamination of coal-based ethanol (containing impurities such as ester compounds, polymers, and pyridine bases at a content of 500 ppm or less) to produce triethylamine, the catalyst being CoRe / Al2O3(R)-2. The catalyst comprises an active component and a carrier, wherein the active components are cobalt and rhenium, and the carrier is an Al2O3(R)-2 carrier. The cobalt content is 10 wt.%, and the rhenium content is 0.5 wt.%, based on the weight percentage of the catalyst.

[0106] The catalyst is prepared according to the following method:

[0107] (1) Preparation of Al2O3(R)-2 carrier: rod-shaped alumina (specific surface area and pore volume are 110m 2 / g and 0.530cm 3 / g, the length / diameter ratio of the crystal is 5) and sesbania powder are mixed and kneaded in a weight ratio of 98:2, and then dried at 120°C and calcined at 500°C for 3h;

[0108] (2) Cobalt nitrate and ammonium rhenate were weighed according to the contents of the active components cobalt and rhenium, and the cobalt nitrate and ammonium rhenate were dissolved in water to obtain an impregnation solution. The Al2O3(R)-2 carrier was placed in the impregnation solution and impregnated in a closed manner at 90°C for 2 hours; dried at 110°C for 12 hours, and then calcined at 350°C in a mixed atmosphere of nitrogen and argon (nitrogen and argon molar ratio of 6:4) for 5 hours, hydrogen was introduced, and reduced at 350°C for 30 hours to obtain a catalyst CoRe / Al2O3(R)-2 (nitrogen protection) with cobalt and rhenium contents of 10wt.% and 0.5wt.%, respectively.

[0109] The performance of the catalyst CoRe / Al2O3(R)-2 in the hydroamination of coal-based ethanol to triethylamine was evaluated in a homemade small-scale reactor. The reactor had a diameter of 9 mm and a catalyst loading of 8 g. Under ammonia conditions, the temperature was raised to 120°C at a rate of 10°C / min, and coal-based ethanol was introduced for 100 hours. The reaction conditions were: temperature of 120°C, pressure of 0.8 MPa, and a coal-based ethanol weight space velocity of 0.08 h / min. -1 The molar ratio of coal-based ethanol to ammonia was 6:1, the molar ratio of coal-based ethanol to diethylamine was 3:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC. The specific evaluation results are shown in Table 1.

[0110] Example 3

[0111] A catalyst for the hydroamination of coal-based ethanol (containing impurities such as ester compounds, polymers, and pyridine bases at a content of 1500 ppm or less) to produce triethylamine, the catalyst being CoRe / Al2O3(R)-3. The catalyst comprises an active component and a carrier, wherein the active components are cobalt and rhenium, and the carrier is an Al2O3(R)-3 carrier. The cobalt content is 20 wt.%, and the rhenium content is 0.25 wt.%, based on the weight percentage of the catalyst.

[0112] The catalyst is prepared according to the following method:

[0113] (1) Preparation of Al2O3(R)-3 carrier: rod-shaped alumina (specific surface area and pore volume are 130m 2 / g and 0.460cm 3 / g, the length / diameter ratio of the crystal is 20) and sesbania powder are mixed and kneaded in a weight ratio of 98:2, and then dried at 120°C and calcined at 500°C for 3h;

[0114] (2) Cobalt nitrate and ammonium rhenate were weighed according to the contents of the active components cobalt and rhenium, and the cobalt nitrate and ammonium rhenate were dissolved in water to obtain an impregnation solution. The Al2O3(R)-3 carrier was placed in the impregnation solution and impregnated in a closed manner at 60°C for 5 hours; dried at 110°C for 6 hours, and then calcined at 400°C in a mixed atmosphere of nitrogen and helium (nitrogen and helium molar ratio of 8:2) for 3 hours, and hydrogen was introduced, and reduced at 400°C for 15 hours to obtain a catalyst CoRe / Al2O3(R)-3 with cobalt and rhenium contents of 20wt.% and 0.2wt.%, respectively.

[0115] The performance of the CoRe / Al2O3(R)-3 catalyst in the hydroamination of coal-based ethanol to triethylamine was evaluated in a small-scale reactor. The reactor diameter was 9 mm, the catalyst loading was 8 g, and the temperature was raised to 200°C at a rate of 10°C / min under ammonia conditions. Coal-based ethanol was introduced for 100 hours. The reaction conditions were: temperature 200°C, pressure 2.0 MPa, and a coal-based ethanol weight space velocity of 0.3 h-1. -1 The molar ratio of coal-based ethanol to ammonia was 4:1, the molar ratio of coal-based ethanol to diethylamine was 4:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC. The specific evaluation results are shown in Table 1.

[0116] Example 4

[0117] A catalyst for the hydroamination of coal-based ethanol (containing impurities such as ester compounds, polymers, and pyridine bases at a content of 8000 ppm or more) to produce triethylamine. The catalyst is CoRe / Al2O3(R)-4 and comprises an active ingredient and a carrier. The active ingredients are cobalt and rhenium, and the carrier is an Al2O3(R)-4 carrier. The cobalt content is 30 wt.%, and the rhenium content is 0.4 wt.%, based on the weight percentage of the catalyst.

[0118] The catalyst is prepared according to the following method:

[0119] (1) Preparation of Al2O3(R)-4 carrier: rod-shaped alumina (specific surface area and pore volume are 280m 2 / g and 0.530cm 3 / g, the length / diameter ratio of the crystal is 30) and sesbania powder are mixed and kneaded in a weight ratio of 98:2, and then dried at 110°C and calcined at 500°C for 2h;

[0120] (2) Cobalt nitrate and ammonium rhenate were weighed according to the contents of the active components cobalt and rhenium, and the cobalt nitrate and ammonium rhenate were dissolved in water to obtain an impregnation solution. The Al2O3(R)-4 carrier was placed in the impregnation solution and impregnated in a closed manner at 80°C for 4 hours; dried at 110°C for 8 hours, and then calcined at 450°C in a mixed atmosphere of nitrogen, argon and helium (nitrogen, argon and helium molar ratio of 5:4:1) for 2 hours, and hydrogen was introduced. The catalyst CoRe / Al2O3(R)-4 with cobalt and rhenium contents of 30wt.% and 0.40wt.%, respectively, was obtained.

[0121] The performance of the CoRe / Al2O3(R)-4 catalyst in the hydroamination of coal-based ethanol to triethylamine was evaluated in a small-scale reactor. The reactor was 9 mm in diameter and loaded with 8 g of catalyst. The reactor was heated to 150°C at a rate of 10°C / min under ammonia conditions, and coal-based ethanol was introduced for 100 hours. The reaction conditions were: temperature 150°C, pressure 1.5 MPa, and a coal-based ethanol weight space velocity of 0.2 h / min. -1 The molar ratio of coal-based ethanol to ammonia was 3:1, the molar ratio of coal-based ethanol to diethylamine was 4:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC. The specific evaluation results are shown in Table 1.

[0122]

[0123] Any slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A catalyst, characterized in that The catalyst includes a carrier and an active component supported on the carrier; The active component includes an active element; The active elements are cobalt and rhenium; The carrier is rod-shaped alumina; The aspect ratio of the rod-shaped alumina is 5-30.

2. The catalyst according to claim 1, characterized in that The aspect ratio of the rod-shaped alumina is 10 to 20; Preferably, the mass of the cobalt is 10-30 wt.% of the mass of the catalyst, and the mass of the rhenium is 0.1-0.5 wt.% of the mass of the catalyst. The masses of the cobalt and rhenium are calculated based on the mass of the cobalt and rhenium elements.

3. The method for preparing the catalyst according to any one of claims 1 to 2, characterized in that: The preparation method comprises: In a closed reactor, the carrier is impregnated with a mixture containing a cobalt precursor and a rhenium precursor, and then dried, calcined, and reduced to obtain the catalyst; The carrier is prepared by mixing and kneading rod-shaped aluminum oxide powder.

4. The preparation method according to claim 3, characterized in that The cobalt precursor is cobalt nitrate; Preferably, the rhenium precursor is ammonium rhenate; Preferably, the mixture further comprises a solvent, and the solvent is water.

5. The preparation method according to claim 3, characterized in that The impregnation is an equal volume closed impregnation; Preferably, the immersion temperature is 60-90°C and the immersion time is 2-5 hours; Preferably, the drying temperature is 110-120°C and the drying time is 6-12 hours; Preferably, the calcination atmosphere is an inert atmosphere; Preferably, the inert atmosphere is selected from at least one of nitrogen, argon and helium; Preferably, the calcination temperature is 350-500° C., and the calcination time is 2-5 hours.

6. The preparation method according to claim 3, characterized in that The reducing atmosphere is hydrogen; Preferably, the reduction temperature is 350-500° C., and the reduction time is 10-30 h.

7. A method for preparing triethylamine by hydroamination of coal-based ethanol, characterized in that: The method comprises: The raw materials containing coal-based ethanol, hydrogen, ammonia and diethylamine are contacted with a catalyst to react to obtain a product containing ethylamine; The catalyst is selected from the catalyst according to any one of claims 1 to 2.

8. The method according to claim 7, characterized in that The molar ratio of the coal-based ethanol to the ammonia is 2 to 6:1; Preferably, the molar ratio of the coal-based ethanol to the diethylamine is 3 to 6:1; Preferably, the molar ratio of the hydrogen to the coal-based ethanol is 1 to 5:

1.

9. The method according to claim 7, characterized in that The weight space velocity of the coal-based ethanol is 0.08 to 0.3 h -1 .

10. The method according to claim 7, characterized in that The reaction pressure is 0.8-2.0 MPa; Preferably, the reaction temperature is 120-200°C.

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