A process for the synthesis of amides / nitriles / amines from alcohols

Abstract

This application discloses a method for synthesizing amides / nitriles / amines from alcohols, comprising the following steps: S1, reacting a mixture containing alcohol, CO, and catalyst I to obtain an intermediate; S2, reacting a mixture containing the above intermediate, an ammonia source, and catalyst II to obtain a product; wherein the intermediate is at least one selected from ethers, carboxylic esters, and carboxylic acids; and the product is at least one selected from amides, nitriles, and amines. The alcohol conversion route provided by this application has high reaction efficiency, high product yield, and good product distribution adjustability, making it suitable for continuous, stable, and large-scale production of multiple products.

Description

Technical Field

[0001] This application relates to a method for synthesizing amides / nitriles / amines from alcohols, belonging to the new technology field of chemical production and manufacturing. Background Technology

[0002] Alcohols are important chemical raw materials that can be used to synthesize various downstream products. However, alcohols are highly reactive and, when used as raw materials, they often undergo various reactions such as dehydroxylation, intermolecular dehydration, and dehydrogenation-disproportionation under the influence of temperature and catalysts, thereby producing impurities such as alkenes, ethers, aldehydes, esters, and acids.

[0003] In typical conversion reactions, the aforementioned impurities can negatively impact the conversion of alcohols to the target product, reducing the selectivity of alcohol-to-target product conversion. Furthermore, these impurities can also negatively affect certain catalysts in the alcohol conversion process. Therefore, there is a need to develop new catalytic reaction processes that are insensitive to alcohol-related impurities. Summary of the Invention

[0004] This application provides a method for synthesizing amides / nitriles / amines from alcohols. This method has high alcohol conversion efficiency, high product yield, and good product distribution adjustability, and is suitable for continuous, stable, and large-scale production of multiple products.

[0005] A method for synthesizing amides / nitriles / amines from alcohols includes the following steps:

[0006] S1. React the mixture containing alcohol, CO, and catalyst I into reaction I to obtain the intermediate;

[0007] S2. React the mixture containing the above intermediate, ammonia source, and catalyst II into product II.

[0008] The intermediate is at least one of ethers, carboxylic acid esters, and carboxylic acids;

[0009] The product is at least one of amides, nitriles, and amines.

[0010] Optionally, in step S1, the mixture also includes carrier gas I.

[0011] Optionally, the carrier gas I is selected from at least one of N2, H2, and CO2.

[0012] The gas in reaction I refers to one of CO, CO / N2, CO / H2, CO / CO2, or CO2 / H2.

[0013] Optionally, in step S1, the alcohol is at least one of compounds having the general formula R1-OH;

[0014] Where R1 is C nH 2n+1 The carbon chain structure, where n is a positive integer between 1 and 6.

[0015] Alternatively, the structure of R1- is as follows:

[0016]

[0017] .

[0018] Optionally, in step S1, the catalyst I is a supported catalyst.

[0019] Optionally, the support for the supported catalyst is at least one of the silica-alumina molecular sieves having MOR, MFI, FER, and FAU structures.

[0020] Optionally, the metal support of the supported catalyst is at least one of Rh, Pt, Ru, Pd, Au, and Ag.

[0021] Optionally, the metal loading is 0.01%-1.0%.

[0022] Optionally, the metal loading is independently selected from any value or a range between 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.20%, 0.30%, 0.40%, 0.50%, 0.60%, 0.70%, 0.80%, 0.90%, and 1.00%.

[0023] The metal loading mentioned above refers to the ratio of the mass of the metal to the total mass of the catalyst.

[0024] Optionally, in step S1, the structural formula of the intermediate is selected from any of the following structures:

[0025] ;

[0026] Among them, R2 and R3 are independently H or R1.

[0027] That is, the alcohol reacts with CO under a certain atmosphere to produce a product containing the above structure.

[0028] R2 and R3 have the same number of carbon atoms as alcohols; R2 and R3 are selected from H or one or both of the structures described in R1.

[0029] Optionally, in step S1, the ratio of the total moles of CO and carrier gas I to the moles of the alcohol is 1-20:1.

[0030] Optionally, the ratio of the total number of moles of CO and the total number of moles of carrier gas I to the total number of moles of the alcohol is independently selected from any value or a range between 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, and 20:1.

[0031] Optionally, in step S1, the conditions for reaction I are as follows:

[0032] The temperature ranges from 100 to 500 ℃.

[0033] Optionally, the temperature is independently selected from any value or a range between 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, and 500 ℃.

[0034] Optionally, in step S1, the pressure of reaction I is 0.1-5.0 MPa.

[0035] Optionally, the pressure of reaction I is independently selected from any value or a range between any two of 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa, 4.5 MPa, and 5.0 MPa.

[0036] Optionally, in step S1, the mass hourly space velocity is 0.1-5 h. -1 .

[0037] Optionally, the mass space velocity is independently selected from 0.1 h. -1 0.2 h -1 0.3 h -1 0.4 h -1 0.5 h -1 0.6 h -1 0.7 h -1 0.8 h -1 0.9 h -1 1.0 h -1 1.5 h -1 2.0 h -1 2.5 h -1 3.0 h -1 3.5 h -14.0 h -1 4.5h -1 5.0 h -1 Any value in the range or any value between the two.

[0038] Optionally, in step S2, the ammonia source is selected from at least one of ammonia, urea, ammonium bicarbonate, and ammonium carbonate.

[0039] Optionally, in step S2, the catalyst is selected from at least one of silica, alumina, molecular sieve, cation exchange resin, and supported inorganic acid.

[0040] Optionally, in step S2, the silicon oxide contains a metal component.

[0041] Optionally, in step S2, at least one of the metal components Pt, Pd, Ru, and Rh has a mass content between 0.001% and 0.3%.

[0042] Optionally, in step S2, at least one of the metal components Ni, Cu, and Zn has a mass content between 0.001% and 1%.

[0043] Optionally, in step S2, the inorganic acid in the supported inorganic acid is selected from at least one of sodium bisulfate, sodium hydrogen phosphate, AlCl3, and heteropolyacids;

[0044] The support in the supported inorganic acid is selected from at least one of silica, diatomaceous earth and kaolin.

[0045] The weight percentage of inorganic acid in the supported inorganic acid is 5%-25%.

[0046] Optionally, in step S2, the molar ratio of the ammonia source to the intermediate is 1-50:1.

[0047] Optionally, in step S2, the molar ratio of the ammonia source to the intermediate is independently selected from any value or a range between any two of the following: 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, and 50:1.

[0048] That is, the total molar ratio of the ammonia gas generated by the ammonia source to the material system of alcohols / ethers / carboxylic acid esters / carboxylic acids is 1-50:1.

[0049] Optionally, step S2 may also include carrier gas II.

[0050] Optionally, the carrier gas II is selected from at least one of CO, H2, CO2, and N2.

[0051] Optionally, in step S2, the total molar ratio of the carrier gas II to the material system is 1-20:1.

[0052] The material system refers to the system of alcohols / ethers / carboxylic acid esters / carboxylic acids.

[0053] Optionally, in step S2, the conditions for reaction II are as follows:

[0054] The temperature ranges from 100 to 500 ℃.

[0055] Optionally, the temperature is independently selected from any value or a range between 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, and 500 ℃.

[0056] Optionally, in step S2, the pressure of reaction II is 0.1-5.0 MPa.

[0057] Optionally, the pressure of reaction II is independently selected from any value or a range between any two of 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa, 4.5 MPa, and 5.0 MPa.

[0058] Optionally, in step S2, the total mass hourly space velocity of the material system is 0.1-10 h⁻¹. -1 .

[0059] Optionally, the mass space velocity is independently selected from 0.1 h. -1 0.2 h -1 0.3 h -1 0.4 h -1 0.5 h -1 0.6 h -1 0.7 h -1 0.8 h -1 0.9 h -1 1.0 h -1 1.5 h -1 2.0 h -1 2.5 h -1 3.0 h -1 3.5 h -1 4.0 h -1 4.5h-1 5.0 h -1 5.5 h -1 6.0 h -1 6.5 h -1 7.0 h -1 7.5 h -1 8.0 h -1 8.5 h -1 9.0 h -1 9.5 h -1 10.0 h -1 Any value in the range or any value between the two.

[0060] Optionally, reaction I and reaction II can be carried out in one or more reactors;

[0061] The reactor is selected from at least one of a fixed-bed reactor and a batch reactor.

[0062] Optionally, after reaction II, the unreacted material is placed in reaction I and / or reaction II for recycling.

[0063] That is, unreacted alcohols and other gaseous mixtures are recycled to the inlet of reactor I, and amides are recycled to the inlet of reactor II.

[0064] According to one embodiment of this application, the method includes the following steps:

[0065] 1) To generate a material system containing ethers / carboxylic acid esters / carboxylic acids by reacting alcohols with a selected atmosphere and catalyst;

[0066] 2) The system containing alcohols / ethers / carboxylic acid esters / carboxylic acid materials is reacted with an ammonia source under a selected reaction atmosphere and catalyst to generate amides, nitriles, and amines with correspondingly increased carbon numbers;

[0067] 3) Unconverted gaseous materials can be recycled and reconverted with alcohols / ethers.

[0068] The alcohol is at least one of the compounds having the chemical formula R1-OH (R1 can be C1 with 1-6 carbon atoms). n H 2-1 (carbon chain structure).

[0069] The alcohol reacts with CO under a certain atmosphere to produce a product containing the following structure, wherein R2 and R3 have the same number of carbon atoms as the alcohol:

[0070] R2 and R3 are selected from H or one or both of the structures described in R1.

[0071] Alcohols react with a catalyst under a selected atmosphere, wherein the catalyst may be a supported catalyst containing at least one of Rh, Pt, Ru, Pd, Au, and Ag.

[0072] Alcohols react with a catalyst under a selected atmosphere, wherein the catalyst may be a silica-alumina molecular sieve with a MOR, MFI, FER, or FAU structure.

[0073] The alcohols are reacted under a selected atmosphere at a temperature of 100-500°C. o C. Pressure between 0.1 and 5.0 MPa;

[0074] The alcohols are reacted in a selected reaction atmosphere, wherein the reaction atmosphere is one of CO, CO / N2, CO / H2, CO / CO2, or CO2 / H2;

[0075] A material system containing alcohols / ethers / carboxylic acid esters / carboxylic acids reacts with an ammonia source under the action of a catalyst in a selected reaction atmosphere. The catalyst is at least one of silica, alumina, molecular sieve, cation exchange resin, and supported inorganic acid.

[0076] A material system containing alcohols / ethers / carboxylic acid esters / carboxylic acids / selected atmospheres reacts with an ammonia source under a selected reaction atmosphere and with the action of a catalyst, wherein the catalyst is at least one of silicon dioxide, alumina, molecular sieve, cation exchange resin, and supported inorganic acid containing metal components.

[0077] The inorganic acid in the supported inorganic acid is selected from at least one of sodium bisulfate, sodium hydrogen phosphate, AlCl3, and heteropolyacids;

[0078] The support in the supported inorganic acid is selected from at least one of silica, diatomaceous earth, and kaolin; the weight percentage of the inorganic acid in the supported inorganic acid is 5-25%.

[0079] A material system containing alcohols / ethers / carboxylic acid esters / carboxylic acids / selected atmospheres reacts with an ammonia source under a selected reaction atmosphere and with the action of a catalyst containing a metal component, wherein the metal component is at least one of Pt, Pd, Ru, and Rh, and the mass content is between 0.001% and 0.3%.

[0080] A material system containing alcohols / ethers / carboxylic acid esters / carboxylic acids / selected atmospheres reacts with an ammonia source under a selected reaction atmosphere and with the action of a catalyst containing a metal component, wherein the metal component is at least one of Ni, Cu, and Zn, and the mass content is between 0.001% and 1%.

[0081] A material system containing alcohols / ethers / carboxylic acid esters / carboxylic acids reacts with an ammonia source under a selected reaction atmosphere and a catalyst, wherein the selected reaction atmosphere is at least one of CO, H2, CO2, and N2;

[0082] A material system containing alcohols / ethers / carboxylic acid esters / carboxylic acids / a selected atmosphere reacts with an ammonia source under the action of a catalyst at a reaction temperature of 100-500°C. o C, the reaction pressure is 0.1-5.0 MPa;

[0083] The reaction process is carried out in one or more reactors, wherein the reactor is selected from at least one of a fixed-bed reactor and a batch reactor.

[0084] After a material system containing alcohols / ethers / carboxylic acid esters / carboxylic acids / selected atmosphere reacts with an ammonia source under the action of a catalyst, the unreacted gaseous material is directly mixed with the alcohol / ether raw material for recycling.

[0085] The beneficial effects that this application can produce include:

[0086] This application provides a method for synthesizing amides / nitriles / amines from alcohols. This method can directly obtain nitriles, amides, and amines with increased carbon numbers from alcohols. The method has low requirements for various acid / olefin / ether impurities generated during the alcohol conversion process, and the formation of nitriles, amides, and amines is minimally affected by these impurities. The catalyst, raw materials, and products are easily separated and have low corrosiveness to equipment. The reaction conditions are mild, requiring no harsh separation processes, and the operation is user-friendly, suitable for continuous, stable, and large-scale production. This alcohol conversion method achieves high yields of nitriles, amines, and amides. Calculated based on the carbon atom utilization rate of alcohols, the carbon atom yield of the corresponding products can reach over 95%. Detailed Implementation

[0087] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0088] Unless otherwise specified, use conventional testing methods or the testing methods recommended by the instrument.

[0089] Example 1

[0090] 100 g of 0.5 wt% Rh / MFI catalyst was loaded into a fixed-bed reactor. Methanol and a CO / CO2 mixture were introduced into the reactor separately and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of methanol to CO / CO2 mixture was 1:2; the reaction temperature was 250 °C. o C; Reaction pressure 2.0 MPa, mass hourly space velocity (HHSV) of methanol 1.0 h⁻¹ -1After the reaction, the conversion rate of methanol was 95.2%, and the selectivities of methyl acetate and acetic acid were 95.4% and 4.4%, respectively. The resulting mixture containing methanol, methyl acetate, and acetic acid was simultaneously introduced with ammonia into a fixed-bed reactor containing an alumina catalyst. The reaction conditions were as follows: the molar ratio of the mixture to ammonia was 1:10; the reaction temperature was 300°C. o C; Reaction pressure 0.2 MPa, space velocity based on total mass of mixture 1.0 h⁻¹ -1 The mass composition of the reactant was 44.3% methanol, 54.8% acetonitrile, 0.7% acetamide, and 0.2% other impurities. The product was separated to obtain acetonitrile, while unreacted methanol and other gaseous mixtures were recycled to the inlet of the first reactor, and acetamide was recycled to the inlet of the second reactor.

[0091] Example 2

[0092] 100 g of 0.1 wt% Pt / MOR catalyst was loaded into a fixed-bed reactor. Ethanol and a CO / N2 mixture were introduced into the reactor and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of ethanol to CO / CO2 mixture was 1:5; the reaction temperature was 200 °C. o C; Reaction pressure 5.0 MPa, mass hourly space velocity (mass hourly space velocity) of methanol 0.5 h⁻¹ -1 After the reaction, the conversion rate of ethanol was 96.7%, and the selectivities for ethyl propionate and propionic acid were 96.0% and 3.2%, respectively. The resulting mixture containing methanol, ethyl propionate, and propionic acid was simultaneously fed with ammonium bicarbonate into a fixed-bed reactor packed with ZSM-5 molecular sieve catalyst. The reaction conditions were as follows: the molar ratio of the mixture to ammonia was 1:20; the reaction temperature was 350°C. o C; Reaction pressure 0.3 MPa, space velocity based on total mass of mixture 3.0 h⁻¹ -1 The mass composition of the reactant was 54.0% propionitrile, 0.8% propionamide, 44.3% ethanol, 0.5% diethyl ether, and 0.4% other impurities. The product was separated to obtain propionitrile; unreacted ethanol and other gaseous mixtures were recycled to the inlet of the first reactor, and propionamide was recycled to the inlet of the second reactor.

[0093] Example 3

[0094] 100 g of 0.3 wt% Ru / FAU catalyst was loaded into a fixed-bed reactor. Pentanol and a CO2 / H2 mixture were introduced into the reactor separately and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of pentanol to CO2 / H2 mixture was 1:20; the reaction temperature was 500 °C. o C; Reaction pressure 4.0 MPa, mass hourly space velocity (HHSV) of methanol 2.0 h⁻¹ -1After the reaction, the conversion rate of pentanol was 99.2%, and the selectivities for the products methyl hexanoate and hexanoic acid were 97.6% and 2.0%, respectively. The resulting mixture containing hexanol, methyl hexanoate, and hexanoic acid was simultaneously fed with ammonium carbonate into a fixed-bed reactor containing a silica catalyst. The reaction conditions were as follows: the molar ratio of the mixture to ammonia was 1:50; the reaction temperature was 500 °C. o C; Reaction pressure 0.5 MPa, space velocity based on total mass of mixture 5.0 h⁻¹ -1 The mass composition of the reactant was 34.2% methanol, 64.0% hexanonitrile, 0.4% hexanoamide, 1.2% pentanol, and 0.3% other impurities. The product was separated to obtain hexanonitrile, while unreacted pentanol and other gaseous mixtures were recycled to the inlet of the first reactor, and hexanoamide was recycled to the inlet of the second reactor.

[0095] Example 4

[0096] 100 g of 0.8 wt% Pd / FER catalyst was loaded into a fixed-bed reactor. Methanol and CO were introduced into the reactor separately and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of methanol to CO was 1:10; the reaction temperature was 300 °C. o C; Reaction pressure 0.1 MPa, mass hourly space velocity (HHSV) of methanol 1.2 h⁻¹ -1 After the reaction, the conversion rate of methanol was 99.4%, and the selectivity of the products methyl acetate and acetic acid was 97.5% and 2.1%, respectively. The resulting mixture containing methanol, methyl acetate, and acetic acid was simultaneously passed into a fixed-bed reactor containing 20 wt% sodium hydrogen phosphate / silica catalyst, along with ammonia water, under the following conditions: a molar ratio of the mixture to ammonia of 1:15; and a reaction temperature of 350°C. o C; Reaction pressure 0.1 MPa, space velocity 1.5 h⁻¹ based on total mass of mixture. -1 The mass composition of the reactant was 43.4% methanol, 55.8% acetonitrile, 0.4% acetamide, and 0.3% other impurities. The product was separated to obtain acetonitrile, while unreacted methanol and other gaseous mixtures were recycled to the inlet of the first reactor, and acetamide was recycled to the inlet of the second reactor.

[0097] Example 5

[0098] 100 g of 0.5 wt% Au / MFI catalyst was loaded into a fixed-bed reactor. Ethanol and a CO2 / H2 mixture were introduced into the reactor separately and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of ethanol to CO2 / H2 mixture was 1:5; the reaction temperature was 400 °C. o C; Reaction pressure 1.0 MPa, mass hourly space velocity (WHSV) of methanol 1.0 h⁻¹ -1After the reaction, the conversion rate of ethanol was 97.4%, and the selectivity of the products ethyl propionate and propionic acid was 98.7% and 0.6%, respectively. The resulting mixture containing methanol, ethyl propionate, and propionic acid was simultaneously introduced with ammonia into a fixed-bed reactor containing a 25 wt% sodium bisulfate / diatomaceous earth catalyst. The reaction conditions were as follows: the molar ratio of the mixture to ammonia was 1:30; the reaction temperature was 100°C. o C; Reaction pressure 0.4 MPa, space velocity based on total mass of mixture 0.1 h⁻¹ -1 The mass composition of the reactant was 54.0% propionitrile, 0.7% propionamide, 44.8% ethanol, 0.5% diethyl ether, and 0.2% other impurities. The product was separated to obtain propionitrile; unreacted ethanol and other gaseous mixtures were recycled to the inlet of the first reactor, and propionamide was recycled to the inlet of the second reactor.

[0099] Example 6

[0100] 100 g of a 1.0 wt% Ag / FAU catalyst was loaded into a fixed-bed reactor. Methanol and CO were introduced into the reactor separately and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of methanol to CO was 1:1; the reaction temperature was 100 °C. o C; Reaction pressure 4.0 MPa, mass hourly space velocity (mass hourly space velocity) based on methanol 0.1 h⁻¹ -1 After the reaction, the conversion rate of methanol was 98.4%, and the selectivities of methyl acetate, acetic acid, and dimethyl ether were 93.3%, 6.2%, and 0.2%, respectively. The resulting mixture containing methanol, methyl acetate, acetic acid, and dimethyl ether was simultaneously passed into a fixed-bed reactor containing ammonia and hydrogen gas, along with ammonia and hydrogen gas. The reaction conditions were as follows: the molar ratio of the mixture to ammonia and hydrogen gas was 1:1:20; the reaction temperature was 350°C. o C; Reaction pressure 0.1 MPa, space velocity 1.5 h⁻¹ based on total mass of mixture. -1 The mass composition of the reactants was 40.5% methanol, 1.4% acetonitrile, 0.2% acetamide, 57.2% ethylamine, 0.2% dimethyl ether, and 0.3% other impurities. The products were separated to obtain ethylamine, while unreacted methanol and other gaseous mixtures were recycled to the inlet of the first reactor, and acetamide was recycled to the inlet of the second reactor.

[0101] Example 7

[0102] 100 g of 1.0 wt% Pt / MFI catalyst was loaded into a fixed-bed reactor. Ethanol and a CO / N2 mixture were introduced into the reactor separately and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of ethanol to CO / N2 mixture was 1:10; the reaction temperature was 300 °C. oC; Reaction pressure 0.5 MPa, mass hourly space velocity (HHSV) of methanol 1.0 h⁻¹ -1 After the reaction, the conversion rate of ethanol was 98.2%, and the selectivities for the products ethyl propionate, propionic acid, and diethyl ether were 99.2%, 0.4%, and 0.2%, respectively. The resulting mixture containing methanol, ethyl propionate, and propionic acid was simultaneously introduced with ammonia and CO into a fixed-bed reactor containing a 0.001 wt% Pd / 1 wt% Ni / alumina catalyst. The reaction conditions were as follows: the molar ratio of the mixture to ammonia and CO was 1:20:10; the reaction temperature was 300 °C. o C; Reaction pressure 0.2 MPa, space velocity based on total mass of mixture 1.0 h⁻¹ -1 The mass composition of the reactant was 53.5% propionitrile, 0.8% propionamide, 1.3% propylamine, 2.4% ethanol, 41.8% ethylamine, and 0.2% other impurities. The products were separated to obtain propionitrile and ethylamine. The separated ethanol was recycled to the inlet of the first reactor, and the propionamide was recycled to the inlet of the second reactor.

[0103] Example 8

[0104] 100 g of 0.8 wt% Ru / MFI catalyst was loaded into a fixed-bed reactor. Methanol and CO were introduced into the reactor separately and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of methanol to CO was 1:10; the reaction temperature was 400 °C. o C; Reaction pressure 1.0 MPa, mass hourly space velocity (WHSV) of methanol 1.0 h⁻¹ -1 After the reaction, the conversion rate of methanol was 99.4%, and the selectivities for the products methyl acetate, acetic acid, and dimethyl ether were 97.8%, 1.2%, and 0.8%, respectively. The resulting mixture containing methanol, methyl acetate, acetic acid, and dimethyl ether was simultaneously introduced with ammonia and CO2 into a fixed-bed reactor packed with a 0.1 wt% Ru 0.05 wt% Cu / ZSM-5 catalyst. The reaction conditions were as follows: the molar ratio of the mixture to ammonia and CO2 was 1:5:20; the reaction temperature was 400 °C. o C; Reaction pressure 0.4 MPa, space velocity based on total mass of mixture 1.0 h⁻¹ -1 The mass composition of the reactants was 40.6% methanol, 52.4% acetonitrile, 0.4% acetamide, 3.0% ethylamine, 3.2% methylamine, and 0.3% other impurities. The products were separated to obtain acetonitrile, ethylamine, and methylamine. Unreacted methanol and other gaseous mixtures were recycled to the inlet of the first reactor, and acetamide was recycled to the inlet of the second reactor.

[0105] Example 9

[0106] 100 g of 0.8 wt% Ru / MFI catalyst was loaded into a fixed-bed reactor. Methanol and CO were introduced into the reactor separately and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of methanol to CO was 1:10; the reaction temperature was 400 °C. o C; Reaction pressure 1.0 MPa, mass hourly space velocity (WHSV) of methanol 1.0 h⁻¹ -1 After the reaction, the conversion rate of methanol was 99.4%, and the selectivities for the products methyl acetate, acetic acid, and dimethyl ether were 97.8%, 1.2%, and 0.8%, respectively. The resulting mixture containing methanol, methyl acetate, acetic acid, and dimethyl ether was simultaneously introduced with ammonia and H2 into a fixed-bed reactor containing a 0.3 wt% Rh, 1 wt% Ni, and 20 wt% phosphotungstic acid / silica catalyst. The reaction conditions were as follows: the molar ratio of the mixture to ammonia and H2 was 1:5:20; the reaction temperature was 350 °C. o C; Reaction pressure 0.1 MPa, space velocity 1.0 h⁻¹ based on total mass of mixture. -1 The mass composition of the reactants was 1.0% methanol, 0.2% acetonitrile, 0.2% acetamide, 58.2% ethylamine, 40.0% methylamine, and 0.3% other impurities. The products were separated to obtain ethylamine and methylamine. Unreacted methanol and other gaseous mixtures were recycled to the inlet of the first reactor, and acetamide was recycled to the inlet of the second reactor.

[0107] Example 10

[0108] 100 g of 0.1 wt% Ag / MOR catalyst was loaded into a fixed-bed reactor. Ethanol and a CO / H2 mixture were introduced into the reactor separately and reacted simultaneously with the catalyst. The reaction conditions were as follows: the molar ratio of ethanol to CO / H2 mixture was 1:5; the reaction temperature was 200 °C. o C; Reaction pressure 5.0 MPa, mass hourly space velocity (HHSV) of methanol 1.0 h⁻¹ -1 After the reaction, the conversion rate of ethanol was 98.7%, and the selectivities for ethyl propionate, propionic acid, and diethyl ether were 98.1%, 1.1%, and 0.5%, respectively. The resulting mixture containing methanol, ethyl propionate, and propionic acid was simultaneously introduced with ammonia and N2 into a fixed-bed reactor containing a 0.1 wt% Pd, 1 wt% Cu, and 5 wt% AlCl3 / kaolin catalyst. The reaction conditions were as follows: the molar ratio of the mixture to ammonia and N2 was 1:10:5; the reaction temperature was 300 °C. o C; Reaction pressure 0.5 MPa, space velocity 1.0 h⁻¹ based on total mass of mixture. -1The mass composition of the reactant was 54.4% propionitrile, 0.8% propionamide, 43.9% ethanol, 0.5% diethyl ether, and 0.4% other impurities. The product was separated to obtain propionitrile; unreacted ethanol and other gaseous mixtures were recycled to the inlet of the first reactor, and propionamide was recycled to the inlet of the second reactor.

[0109] 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. A method for the synthesis of amides / nitriles / amines from alcohols, characterized in that, Includes the following steps: S1. React the mixture containing alcohol, CO, and catalyst I into reaction I to obtain the intermediate; The mixture also includes carrier gas I; The carrier gas I is selected from at least one of N2, H2, and CO2; Wherein, the alcohol is a compound of the general formula R1-OH, where R1 is C n H 2n+1 The carbon chain structure, where n is a positive integer between 1 and 6; Catalyst I is a supported catalyst; The support for the supported catalyst is at least one of the silica-alumina molecular sieves having MOR, MFI, FER, and FAU structures; The supported catalyst has at least one metal supported on it, namely Rh, Pt, Ru, Pd, Au, and Ag, with a loading amount of 0.01%-0.5%. The reaction I is carried out at a temperature of 250-300 °C, a pressure of 1.0-2.0 MPa, and a mass space velocity of 0.5-3 h -1 ; S2. The intermediate obtained in step S1 is reacted directly with an ammonia source in the presence of catalyst II without separation to obtain the product. Wherein, catalyst II is selected from alumina or molecular sieve; The conditions for reaction II are: temperature 200-400 ℃; pressure 0.1-3.0 MPa; The intermediate is at least one of ethers, carboxylic acid esters, and carboxylic acids; The product is at least one of amides, nitriles, and amines.

2. The method of claim 1, wherein, The structural form of R1- is as follows: 。 3. The method according to claim 1, characterized in that, In step S1, the structural formula of the intermediate is selected from any one of the following structures: 、 、 、 ； Among them, R2 and R3 are independently H or R1.

4. The method of claim 1, wherein, In step S1, the ratio of the total molar number of CO and the carrier gas I mixture to the molar number of the alcohol is 1-20:

1.

5. The method of claim 1, wherein, In step S2, the ammonia source is selected from at least one of ammonia, urea, ammonium bicarbonate, and ammonium carbonate.

6. The method of claim 1, wherein, In step S2, the molar ratio of the ammonia source to the intermediate is 1-50:

1.

7. The method of claim 6, wherein, Step S2 also includes carrier gas II.

8. The method of claim 7, wherein, The carrier gas II is selected from at least one of CO, H2, CO2, and N2.

9. The method of claim 7, wherein, In step S2, the total molar ratio of carrier gas II to the material system is 1-20:

1.

10. The method of claim 1, wherein, In step S2, the total mass space velocity of the material system is 0.1-10 h -1 .

11. The method of claim 10, wherein, Reaction I and Reaction II are carried out in one or more reactors; The reactor is selected from at least one of a fixed-bed reactor and a batch reactor.

12. The method of claim 10, wherein, After reaction II, the unreacted material is placed in reaction I and / or reaction II for recycling and transformation.

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