Aluminum-based catalyst for producing triethylamine through reaction of coal-based ethanol and diethylamine as well as preparation method and application of aluminum-based catalyst

Abstract

The invention discloses an aluminum-based catalyst for producing triethylamine through reaction of coal-based ethanol and diethylamine. The active component is loaded on the carrier; the rod-like morphology is fully utilized, the dispersity of active metal can be effectively improved, the isolation effect of Sn is achieved, after hydrogen reduction, oxidation-state cobalt becomes reduction-state cobalt more easily, distribution of the reduction-state cobalt in rod-like aluminum oxide is more uniform, agglomeration is not prone to occurring in the reaction process, and the reaction efficiency is improved. The diffusion of reactants and products in the catalyst and the improvement of the reaction activity of the catalyst are facilitated; when the catalyst is used for producing triethylamine through reaction of coal-based ethanol and diethylamine, compared with a CoSn / Al2O3 (irregular morphology) catalyst, the selectivity of triethylamine can be obviously improved. The active components are elemental cobalt and elemental tin.

Description

Technical Field

[0001] This application relates to an aluminum-based catalyst for the reaction of coal-based ethanol and diethylamine to produce triethylamine, belonging to the field of catalysts. Background Technology

[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 pharmaceuticals, pesticides, chemical auxiliaries, military industry and new energy industries.

[0003] Currently, ethylamine is mainly obtained globally through the hydroamination of bioethanol. However, my country's bioethanol production is limited and its price is high. The successful development and industrial production of coal-based ethanol (>3 million tons / year), which is cheaper, provides a raw material guarantee and price advantage for the implementation of this project.

[0004] Currently, the market demand for monoethylamine, diethylamine, and triethylamine is in a ratio of 1:1:4, with triethylamine having a higher added value. To increase the production of triethylamine, existing ethylamine production processes utilize large quantities of diethylamine to promote triethylamine formation. The recycled diethylamine reacts with ethanol in the reactor to produce triethylamine. While this method achieves the goal of producing more triethylamine, the generated triethylamine must pass through gas-liquid separators, deammoniation towers, monoethylamine towers, and diethylamine towers sequentially. These processes are largely ineffective in separating triethylamine and increase the size and energy consumption of this equipment. Furthermore, the recycling of diethylamine effectively increases the catalyst space velocity, affecting the catalyst's activity and stability.

[0005] To address the problems of 1) increased separation equipment size and energy consumption caused by the large-scale recycling of diethylamine in existing ethylamine production processes to produce more triethylamine, and 2) decreased catalyst stability, a method for producing ethylamine by converting diethylamine to triethylamine in a separately designed reactor is proposed. This method involves the reaction of coal-based ethanol and diethylamine to prepare highly selective triethylamine. Similar to the synthesis of primary amines, the key to the catalytic amination synthesis of secondary or tertiary amines from alcohols lies in the development of catalysts with excellent reaction performance.

[0006] J. Mol. Catal. A, 2005(241)175 reported the synthesis of triethylamine from ethylene and diethylamine using LiNEt2-TMED as a catalyst at 70 bar and 140 °C, achieving a yield of 83%. However, this reaction involved low catalyst activity and a large catalyst dosage, leading to increased production costs and hindering industrial production. Therefore, it is essential to propose a short, easily separable, highly efficient, energy-saving, and low-cost synthetic route for triethylamine.

[0007] Chinese patent CN102614892B discloses a supported catalyst for the synthesis of triethylamine, using calcined gama-alumina (irregular morphology) as a support, with a specific surface area of ​​230–250 m². 2 / g, with a pore size of 10–11.5 nm. Active components, consisting of nickel, copper, and palladium, are loaded onto a support; nickel, copper, and palladium account for 15–25%, 5–12%, and 1–3% of the total weight, respectively. Ethylamine and diethylamine are mixed in a mixing tank to obtain a mixture. This mixture is then vaporized and passed through a fixed-bed reactor containing an activated supported catalyst. A disproportionation reaction is carried out under hydrogen conditions. After the reaction is complete, the mixture is condensed, and the condensate is collected and distilled to obtain triethylamine.

[0008] For the reaction of coal-based ethanol and diethylamine to produce triethylamine, impurities such as esters, polymers and pyridine bases in coal-based ethanol affect the reaction performance of the catalyst. No literature or patent reports have been found on how to develop a catalyst that is resistant to impurities, operates at low temperature, has high activity and high selectivity for triethylamine in the reaction of coal-based ethanol and diethylamine to produce triethylamine. Summary of the Invention

[0009] According to one aspect of this application, an aluminum-based catalyst is provided for the reaction of coal-based ethanol and diethylamine to produce triethylamine, said aluminum-based catalyst comprising a support and an active component supported on said support;

[0010] The carrier is rod-shaped alumina;

[0011] The active components are elemental cobalt and elemental tin.

[0012] The aspect ratio of the rod-shaped alumina is 5 to 30.

[0013] Optionally, the aspect ratio of the rod-shaped alumina is independently selected from any value of 5, 10, 15, 20, 25, 30 or a range between any two of the above.

[0014] In the aluminum-based catalyst, the mass content of elemental cobalt is 10-30 wt%.

[0015] Optionally, in the aluminum-based catalyst, the mass content of the elemental cobalt is independently selected from any value of 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 28 wt.%, 30 wt.%, or a range between any two of the above.

[0016] In the aluminum-based catalyst, the mass content of elemental tin is 0.25–5 wt%.

[0017] Optionally, the mass content of the elemental tin is independently selected from any value of 0.25 wt.%, 0.5 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, or a range between any two of the above.

[0018] According to another aspect of this application, a method for preparing the above-mentioned aluminum-based catalyst for the reaction of coal-based ethanol and diethylamine to produce triethylamine is provided, comprising the following steps:

[0019] In a closed reactor, the support is immersed in an ethanol solution containing cobalt precursor and tin precursor, then dried, calcined, and reduced to obtain the catalyst.

[0020] The carrier was prepared by kneading and molding rod-shaped alumina powder.

[0021] The cobalt precursor is selected from at least one of cobalt nitrate and cobalt chloride;

[0022] The tin precursor is selected from at least one of tin dichloride and tin tetrachloride.

[0023] The impregnation is an equal-volume, closed impregnation.

[0024] The impregnation temperature is 60–90°C.

[0025] 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.

[0026] The soaking time is 2 to 5 hours.

[0027] Optionally, the immersion time is independently selected from any value of 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or a range between any two of the above.

[0028] The drying temperature is 110–120°C.

[0029] Optionally, the drying temperature is independently selected from any value of 110℃, 112℃, 115℃, 118℃, 120℃ or a range between any two of the above.

[0030] The drying time is 6 to 12 hours.

[0031] Optionally, the drying time can be independently selected from any value of 6h, 7h, 8h, 9h, 10h, 11h, 12h or a range between any two of the above.

[0032] The roasting temperature is 350–500°C.

[0033] Optionally, the roasting temperature can be independently selected from any value of 350°C, 400°C, 450°C, 500°C, or a range between any two of the above.

[0034] The roasting time is 2 to 5 hours.

[0035] Optionally, the roasting time can be independently selected from any value of 2h, 3h, 4h, 5h or a range between any two of the above.

[0036] The reducing atmosphere is a hydrogen atmosphere;

[0037] The reduction temperature is 350–500°C.

[0038] Optionally, the reduction temperature is independently selected from any value of 350°C, 400°C, 450°C, 500°C, or a range between any two of the above.

[0039] The reduction time is 10 to 30 hours.

[0040] Optionally, the restoration time is independently selected from any value among 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, and 30h, or a range between any two of the above.

[0041] According to another aspect of this application, a method for producing triethylamine by reacting coal-based ethanol and diethylamine is provided, comprising the following steps:

[0042] A raw material containing coal-based ethanol, hydrogen, and diethylamine is reacted with a catalyst to obtain a product containing triethylamine.

[0043] The catalyst is selected from the catalysts mentioned above.

[0044] The molar ratio of coal-based ethanol to diethylamine is 0.5 to 2:1;

[0045] The molar ratio of hydrogen to coal-based ethanol is 1 to 5:1;

[0046] The weight hourly space velocity (WHSV) of the coal-based ethanol is 0.1–0.3 h⁻¹. -1 ;

[0047] The reaction pressure is 0.8–2.0 MPa;

[0048] The reaction temperature is 140–200°C.

[0049] As an optional implementation, this application is achieved through the following technical solution:

[0050] The catalyst preparation method includes: immersing the support in an ethanol solution containing cobalt and tin precursors at a certain temperature in a sealed environment, and then drying, calcining, and reducing to obtain the catalyst.

[0051] The cobalt precursor is cobalt nitrate; the tin precursor is tin dichloride and / or tin tetrachloride.

[0052] The carrier is prepared by kneading rod-shaped alumina powder.

[0053] The catalyst preparation method is as follows: rod-shaped alumina powder is kneaded to obtain Al2O3 (rod-shaped) support, then an ethanol solution of cobalt nitrate and tin chloride is impregnated in an equal volume sealed manner at a certain temperature, and then dried, calcined and reduced to obtain the desired CoSn / Al2O3 (rod-shaped) catalyst.

[0054] In this application, the content of impurities such as trace esters, polymers and pyridine bases in "coal-based ethanol" is 0 to 8000 ppm;

[0055] The carrier is rod-shaped alumina, denoted as "R".

[0056] The beneficial effects that this application can produce include:

[0057] The CoSn / Al2O3(R) catalyst prepared in this invention fully utilizes the rod-shaped morphology to effectively improve the dispersion of active metals and the isolation effect of Sn. After hydrogen reduction, the oxidized cobalt is more easily converted into reduced cobalt and its distribution in the rod-shaped alumina is more uniform. It is less prone to agglomeration during the reaction, which is beneficial to the diffusion of reactants and products in the catalyst and the improvement of the catalyst's reaction activity. When used in the reaction of coal-based ethanol and diethylamine to produce triethylamine, the triethylamine selectivity can be significantly improved compared with the CoSn / Al2O3 (irregular morphology) catalyst. Detailed Implementation

[0058] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0059] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0060] The analysis method in the embodiments of this application is as follows:

[0061] The aspect ratio of the rod-shaped alumina crystals was obtained by SEM (HITACHI SU1510).

[0062] The weight content of cobalt and tin in the catalyst was determined by XRF (PANAlytical).

[0063] Gas chromatography with an Agilent 7890A was used to analyze the raw materials and products.

[0064] In the embodiments of this application, the catalyst activity evaluation indicators, namely ethanol conversion rate, ammonia conversion rate, and triethylamine selectivity, are all calculated based on weight:

[0065] Ethanol conversion rate:

[0066]

[0067] Triethylamine selectivity:

[0068]

[0069] In the above formula, m represents weight.

[0070] In the following embodiments, "A" in Al2O3(A) refers to an irregular morphology.

[0071] Comparative Example 1

[0072] A catalyst for the reaction of coal-based ethanol (containing impurities such as esters, polymers, and pyridine bases at a concentration of ~3000 ppm) and diethylamine to produce triethylamine, wherein the catalyst is CoSn / Al2O3(A)-1, the catalyst comprises an active component and a support, wherein the active component is cobalt and tin, and the support is an Al2O3(A)-1 support; the cobalt content is 25 wt.% and the tin content is 2 wt.% by weight of the catalyst.

[0073] The catalyst was prepared according to the following method:

[0074] (1) Preparation of Al2O3(A)-1 support: Irregularly shaped alumina (with a specific surface area and pore volume of 224 m²) was used as a support. 2 / g and 0.509cm 3 / g) Hetian ore powder is mixed and kneaded at a weight ratio of 98:2, then dried at 120℃ and calcined at 500℃ for 3 hours;

[0075] (2) According to the content of active components cobalt and tin, weigh cobalt nitrate and tin dichloride, dissolve cobalt nitrate and tin dichloride in ethanol to obtain an impregnation solution, place Al2O3(A)-1 support in the impregnation solution, impregnate in a sealed manner at 70°C for 3h; dry at 120°C for 6h, then calcine at 500°C in an air atmosphere for 2h, introduce hydrogen gas, and reduce at 500°C for 10h to obtain catalyst CoSn / Al2O3(A)-1 with cobalt and tin contents of 25wt% and 2wt% respectively (nitrogen protection).

[0076] The performance of the catalyst CoSn / Al₂O₃(A)-1 in the production of triethylamine from coal-based ethanol and diethylamine was evaluated in a small-scale reactor. The reactor diameter was 12 mm, and the catalyst loading was 8 g. Under diethylamine conditions, the temperature was increased to 150 °C at a rate of 10 °C / min, followed by the introduction of coal-based ethanol. The evaluation time was 50 h. The reaction conditions were: temperature 150 °C, pressure 1.5 MPa, and coal-based ethanol weight hourly space velocity (WHSV) 0.2 h⁻¹. -1 The molar ratio of coal-based ethanol to diethylamine was 1:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC, and the specific evaluation results are shown in Table 1. The reaction performance was evaluated when coal-based ethanol was replaced with bioethanol under the same catalyst and reaction conditions, as shown in Table 1.

[0077] Comparative Example 2

[0078] A catalyst for the reaction of coal-based ethanol (containing impurities such as esters, polymers, and pyridine bases at a concentration of ~3000 ppm) and diethylamine to produce triethylamine, wherein the catalyst is Co / Al2O3(R)-1, the catalyst comprises an active component and a support, wherein the active component is cobalt, and the support is an Al2O3(R)-1 support; the cobalt content is 25% wt.% based on the weight percentage of the catalyst.

[0079] The catalyst was prepared according to the following method:

[0080] (1) Preparation of Al2O3(R)-1 support: Rod-shaped alumina (with a specific surface area and pore volume of 228 m²) was used as a support. 2 / g and 0.557cm 3 / g, with a length / diameter ratio of 10 for the crystals) and guar gum powder are mixed and kneaded at a weight ratio of 98:2, then dried at 120℃ and calcined at 500℃ for 3 hours;

[0081] (2) According to the content of cobalt active component, cobalt nitrate was weighed and dissolved in ethanol to obtain an impregnation solution. The Al2O3(R)-1 support was placed in the impregnation solution and impregnated in a sealed manner at 70°C for 3 hours. It was then dried at 120°C for 6 hours and calcined at 500°C in an air atmosphere for 2 hours. Hydrogen was introduced and the catalyst Co / Al2O3(R)-1 with a cobalt content of 25 wt.% was obtained (under nitrogen protection).

[0082] The performance of the catalyst Co / Al₂O₃(R)₁ in the production of triethylamine from coal-based ethanol and diethylamine was evaluated using a small-scale reactor. The reactor diameter was 12 mm, and the catalyst loading was 8 g. Under diethylamine conditions, the temperature was increased to 150 °C at a rate of 10 °C / min, followed by the introduction of coal-based ethanol. The evaluation time was 50 h. The reaction conditions were: temperature 150 °C, pressure 1.5 MPa, and coal-based ethanol weight hourly space velocity (WHSV) 0.2 h⁻¹. -1 The molar ratio of coal-based ethanol to diethylamine was 1:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC, and the specific evaluation results are shown in Table 1.

[0083] Comparative Example 3

[0084] A catalyst for the reaction of coal-based ethanol (containing impurities such as esters, polymers, and pyridine bases at a concentration of ~3000 ppm) and diethylamine to produce triethylamine, wherein the catalyst is CoSn / Al2O3(R)-1, the catalyst comprises an active component and a support, wherein the active component is cobalt and tin, and the support is an Al2O3(R)-1 support; the cobalt content is 25 wt.% and the tin content is 2 wt.% by weight of the catalyst.

[0085] The catalyst was prepared according to the following method:

[0086] (1) Preparation of Al2O3(R)-1 support: Rod-shaped alumina (with a specific surface area and pore volume of 228 m²) was used as a support. 2 / g and 0.557cm 3 / g, with a length / diameter ratio of 10 for the crystals) and guar gum powder are mixed and kneaded at a weight ratio of 98:2, then dried at 120℃ and calcined at 500℃ for 3 hours;

[0087] (2) According to the content of active components cobalt and tin, weigh cobalt nitrate and tin dichloride, dissolve cobalt nitrate and tin dichloride in water to obtain an impregnation solution, place the Al2O3(R)-1 support in the impregnation solution, and impregnate it in a sealed manner at 70°C for 3 hours; dry it at 120°C for 6 hours, and then calcine it at 500°C in an air atmosphere for 2 hours, introduce hydrogen gas, and reduce it at 500°C for 10 hours to obtain a catalyst CoSn / Al2O3(R)-H2O (nitrogen protection) with a cobalt content of 25wt.%.

[0088] The performance of the CoSn / Al₂O₃(R)-H₂O catalyst for the hydroamination of coal-based ethanol to triethylamine was evaluated in a small-scale reactor. The reactor diameter was 12 mm, the catalyst loading was 8 g, and the temperature was increased to 150 °C at a rate of 10 °C / min under ammonia atmosphere. Coal-based ethanol was then introduced, and the evaluation time was 50 h. The reaction conditions were: temperature 150 °C, pressure 1.5 MPa, and coal-based ethanol weight hourly space velocity (WHSV) 0.2 h⁻¹. -1 The molar ratio of coal-based ethanol to diethylamine was 1:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC, and the specific evaluation results are shown in Table 1.

[0089] Example 1

[0090] A catalyst for the reaction of coal-based ethanol (containing impurities such as esters, polymers, and pyridine bases at a concentration of ~3000 ppm) and diethylamine to produce triethylamine, wherein the catalyst is CoSn / Al2O3(R)-1, the catalyst comprises an active component and a support, wherein the active component is cobalt and tin, and the support is an Al2O3(R)-1 support; the cobalt content is 25 wt.% and the tin content is 2 wt.% by weight of the catalyst.

[0091] The catalyst was prepared according to the following method:

[0092] (1) Preparation of Al2O3(R)-1 support: Rod-shaped alumina (with a specific surface area and pore volume of 228 m²) was used as a support. 2 / g and 0.557cm 3 / g, with a length / diameter ratio of 10 for the crystals) and guar gum powder are mixed and kneaded at a weight ratio of 98:2, then dried at 120℃ and calcined at 500℃ for 3 hours;

[0093] (2) According to the content of active components cobalt and tin, weigh cobalt nitrate and tin dichloride, dissolve cobalt nitrate and tin dichloride in ethanol to obtain an impregnation solution, place the Al2O3(R)-1 support in the impregnation solution, and impregnate it in a sealed container at 70°C for 3 h; dry it at 120°C for 6 h, then calcine it at 500°C in an air atmosphere for 2 h, introduce hydrogen gas, and reduce it at 500°C for 10 h to obtain a catalyst CoSn / Al2O3(R)-1 with a cobalt content of 25 wt.% and a tin content of 2 wt.% (nitrogen protection).

[0094] The performance of the catalyst CoSn / Al₂O₃(R)₁ in the production of triethylamine from coal-based ethanol and diethylamine was evaluated in a small-scale reactor. The reactor diameter was 12 mm, the catalyst loading was 8 g, and the temperature was increased to 150 °C at a rate of 10 °C / min under ammonia atmosphere. Coal-based ethanol was then introduced, and the evaluation time was 50 h. The reaction conditions were: temperature 150 °C, pressure 1.5 MPa, and coal-based ethanol weight hourly space velocity (WHSV) 0.2 h⁻¹. -1 The molar ratio of coal-based ethanol to diethylamine was 1:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC, and the specific evaluation results are shown in Table 1. The reaction performance was evaluated when coal-based ethanol was replaced with bioethanol under the same catalyst and reaction conditions, as shown in Table 1.

[0095] Example 2

[0096] A catalyst for the reaction of coal-based ethanol (containing impurities such as esters, polymers, and pyridine bases at a concentration of ~500 ppm) and diethylamine to produce triethylamine, wherein the catalyst is CoSn / Al2O3(R)-2, the catalyst comprises an active component and a support, wherein the active component is cobalt and tin, and the support is an Al2O3(R)-2 support; the cobalt content is 10 wt.% and the tin content is 5 wt.% by weight of the catalyst.

[0097] The catalyst was prepared according to the following method:

[0098] (1) Preparation of Al2O3(R)-2 support: Rod-shaped alumina (with a specific surface area and pore volume of 110 m²) was used as a support. 2 / g and 0.530cm 3 / g, with a length / diameter ratio of 5 for the crystals) and guar gum powder are mixed and kneaded at a weight ratio of 98:2, then dried at 120℃ and calcined at 500℃ for 3 hours;

[0099] (2) According to the content of active components cobalt and tin, weigh cobalt nitrate and tin tetrachloride, dissolve cobalt nitrate and tin tetrachloride in ethanol to obtain an impregnation solution, place the Al2O3(R)-2 support in the impregnation solution, and impregnate it in a sealed container at 90°C for 2 h; dry it at 110°C for 12 h, then calcine it at 350°C in an air atmosphere for 5 h, introduce hydrogen gas, and reduce it at 350°C for 30 h to obtain a catalyst CoSn / Al2O3(R)-2 with cobalt and tin contents of 10 wt.% and 5 wt.% respectively (nitrogen protection).

[0100] The performance of the catalyst CoSn / Al₂O₃(R)₂ in the hydroamination of coal-based ethanol to triethylamine was evaluated using a self-made small-scale reactor. The reactor diameter was 12 mm, the catalyst loading was 8 g, and the temperature was increased to 140 °C at a rate of 10 °C / min under ammonia atmosphere. Coal-based ethanol was then introduced, and the evaluation time was 50 h. The reaction conditions were: temperature 140 °C, pressure 0.8 MPa, and coal-based ethanol weight hourly space velocity (WHSV) 0.1 h⁻¹. -1 The molar ratio of coal-based ethanol to diethylamine was 0.5:1, and the molar ratio of hydrogen to coal-based ethanol was 1:1. The products were analyzed using an Agilent 7890A GC, and the specific evaluation results are shown in Table 1.

[0101] Example 3

[0102] A catalyst for the reaction of coal-based ethanol (containing impurities such as esters, polymers, and pyridine bases at a content of ~1500 ppm) and diethylamine to produce triethylamine, wherein the catalyst is CoSn / Al2O3(R)-3, the catalyst comprises an active component and a support, wherein the active component is cobalt and tin, and the support is an Al2O3(R)-3 support; the cobalt content is 20 wt.% and the tin content is 0.25 wt.% by weight of the catalyst.

[0103] The catalyst was prepared according to the following method:

[0104] (1) Preparation of Al2O3(R)-3 support: Rod-shaped alumina (with a specific surface area and pore volume of 130 m²) was used as a support. 2 / g and 0.460cm 3 / g, with a length / diameter ratio of 20 for the crystals) and guar gum powder are mixed and kneaded at a weight ratio of 98:2, then dried at 120℃ and calcined at 500℃ for 3 hours;

[0105] (2) According to the content of active components cobalt and tin, weigh cobalt chloride and tin dichloride, dissolve cobalt chloride and tin dichloride in anhydrous ethanol to obtain an impregnation solution, place Al2O3(R)-3 support in the impregnation solution, impregnate in a sealed manner at 60°C for 5h; dry at 110°C for 6h, then calcine at 400°C in air for 3h, introduce hydrogen gas, and reduce at 400°C for 15h to obtain catalyst CoSn / Al2O3(R)-3 with cobalt and tin contents of 20wt.% and 0.25wt.% respectively (nitrogen protection).

[0106] The performance of the catalyst CoSn / Al₂O₃(R)₃ in the hydroamination of coal-based ethanol to triethylamine was evaluated using a small-scale reactor. The reactor diameter was 9 mm, and the catalyst loading was 8 g. Under diethylamine conditions, the temperature was increased to 200 °C at a rate of 10 °C / min, followed by the introduction of coal-based ethanol. The evaluation time was 50 h. The reaction conditions were: temperature 200 °C, pressure 2.0 MPa, and coal-based ethanol weight hourly space velocity (WHSV) 0.3 h⁻¹. -1 The molar ratio of coal-based ethanol to diethylamine was 2:1, and the molar ratio of hydrogen to coal-based ethanol was 3:1. The products were analyzed using an Agilent 7890A GC, and the specific evaluation results are shown in Table 1.

[0107] Example 4

[0108] A catalyst for the reaction of coal-based ethanol (containing impurities such as esters, polymers, and pyridine bases at a concentration of ~8000 ppm) and diethylamine to produce triethylamine, wherein the catalyst is CoSn / Al2O3(R)-4, the catalyst comprises an active component and a support, wherein the active component is cobalt and tin, and the support is an Al2O3(R)-4 support; the cobalt content is 30 wt.% and the tin content is 4 wt.% by weight of the catalyst.

[0109] The catalyst was prepared according to the following method:

[0110] (1) Preparation of Al2O3(R)-4 support: Rod-shaped alumina (with a specific surface area and pore volume of 280 m²) was used as a support. 2 / g and 0.530cm 3 / g, with a length / diameter ratio of 30) and guar gum powder were mixed and kneaded at a weight ratio of 98:2, then dried at 110℃ and calcined at 500℃ for 2 hours;

[0111] (2) According to the content of active components cobalt and tin, weigh cobalt nitrate, tin dichloride and tin tetrachloride, dissolve cobalt nitrate, tin dichloride and tin tetrachloride in ethanol to obtain an impregnation solution, place the Al2O3(R)-4 support in the impregnation solution, impregnate in a sealed manner at 80°C for 4h; dry at 110°C for 8h, then calcine at 450°C in an air atmosphere for 2h, introduce hydrogen gas, and reduce at 400°C for 10h to obtain a catalyst CoSn / Al2O3(R)-4 with cobalt and tin contents of 30wt.% and 4wt.% respectively (nitrogen protection).

[0112] The performance of the catalyst CoSn / Al₂O₃(R)₄ in the hydroamination of coal-based ethanol to triethylamine was evaluated using a small-scale reactor. The reactor diameter was 12 mm, and the catalyst loading was 8 g. Under ammonia conditions, the temperature was increased to 150 °C at a rate of 10 °C / min, followed by the introduction of coal-based ethanol. The evaluation time was 50 h. The reaction conditions were: temperature 150 °C, pressure 1.5 MPa, and coal-based ethanol weight hourly space velocity (WHSV) 0.2 h⁻¹. -1 The molar ratio of coal-based ethanol to diethylamine was 1:1, and the molar ratio of hydrogen to coal-based ethanol was 5:1. The products were analyzed using an Agilent 7890A GC, and the specific evaluation results are shown in Table 1.

[0113] Table 1 Catalyst Reaction Performance

[0114]

[0115] *: Bioethanol (99.99% ethanol), which corresponds to the relevant parameters of bioethanol.

[0116] The experimental results in Table 1 show that, compared with the cobalt-tin supported irregular morphology alumina catalyst prepared by ethanol solvent (Comparative Example 1), the cobalt-supported rod-shaped alumina catalyst (Comparative Example 2) and the cobalt-tin supported rod-shaped alumina catalyst prepared by water solvent (Comparative Example 3), the catalyst provided by the present invention can significantly improve the conversion rate of coal-based ethanol in the reaction of coal-based ethanol and diethylamine to produce triethylamine, as in Example 1;

[0117] The catalysts involved in this invention patent also have good applicability to the conversion of bioethanol (Example 1 vs Example 1*), while the amination conversion of coal-based ethanol on the cobalt-tin supported alumina support catalyst with irregular morphology prepared by ethanol solvent (Comparative Example 1) is worse than that of bioethanol (Comparative Example 1 vs Comparative Example 1*); the catalysts involved in Examples 1 to 4 all have good reaction performance.

[0118] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An aluminum-based catalyst for the reaction of coal-based ethanol and diethylamine to produce triethylamine, characterized in that, The aluminum-based catalyst includes a support and an active component supported on the support; The carrier is rod-shaped alumina; The active components are elemental cobalt and elemental tin.

2. The aluminum-based catalyst according to claim 1, characterized in that, The aspect ratio of the rod-shaped alumina is 5 to 30; Preferably, in the aluminum-based catalyst, the mass content of elemental cobalt is 10-30 wt%. Preferably, in the aluminum-based catalyst, the mass content of elemental tin is 0.25–5 wt%.

3. A method for preparing an aluminum-based catalyst for the reaction of coal-based ethanol and diethylamine to produce triethylamine, as described in claim 1 or 2, characterized in that, Includes the following steps: In a closed reactor, the support is immersed in an ethanol solution containing cobalt precursor and tin precursor, then dried, calcined, and reduced to obtain the catalyst.

4. The preparation method according to claim 3, characterized in that, The cobalt precursor is selected from at least one of cobalt nitrate and cobalt chloride; The tin precursor is selected from at least one of tin dichloride and tin tetrachloride.

5. The preparation method according to claim 3, characterized in that, The impregnation temperature is 60–90°C; The soaking time is 2 to 5 hours.

6. The preparation method according to claim 3, characterized in that, The drying temperature is 110–120°C; The drying time is 6 to 12 hours.

7. The preparation method according to claim 3, characterized in that, The roasting temperature is 350–500°C; The roasting time is 2 to 5 hours.

8. The preparation method according to claim 3, characterized in that, The reducing atmosphere is a hydrogen atmosphere; The reduction temperature is 350–500°C; The reduction time is 10 to 30 hours.

9. A method for producing triethylamine by reacting coal-based ethanol and diethylamine, characterized in that, Includes the following steps: A raw material containing coal-based ethanol, hydrogen, and diethylamine is reacted with a catalyst to obtain a product containing triethylamine. The catalyst is selected from the catalyst described in any one of claims 1 or 2.

10. The method according to claim 9, characterized in that, The molar ratio of coal-based ethanol to diethylamine is 0.5 to 2:1; The molar ratio of hydrogen to coal-based ethanol is 1 to 5:1; The weight hourly space velocity (WHSV) of the coal-based ethanol is 0.1–0.3 h⁻¹. -1 ; The reaction pressure is 0.8–2.0 MPa; The reaction temperature is 140–200°C.

Images