CN100435947C - Catalyst for preparing fatty primary amine by fatty nitrile hydrogenation and application thereof - Google Patents

Abstract

The invention discloses a making method of hydrogenated primary fat amine, which comprises the following steps: setting the molar rate of nickel, cobalt, auxiliary catalyst and rare earth at 100:0.01-2.0:1-15:0.01-1; allocating soluble metal salt into composite solution with density at 0.1-1mol/L; heating to 60-80 deg.c; adding water and hydrazine/metal ion with molar rate at 1-5 and potassium borohydride/metal ion with molar rate at 0.01-0.5; stirring under 60-80 deg.c for 3-5 min; heating; stirring; washing until neutral; extracting into vacuum; drying; reserving in the anhydrous alcohol.

Description

Catalyst, preparation method and application of fatty nitrile hydrogenation to fatty primary amine

technical field

The invention relates to a catalyst, a preparation method and an application for preparing fatty primary amines through hydrogenation of fatty nitriles.

Background technique

Document CN 1088198A discloses a method for preparing primary amines. In this document, the selectivity of primary amine hydrogenation of aliphatic nitriles with supported nickel and/or cobalt catalysts at 140° C. and pressure of 1 MPa NH ₃ +2 MPa H ₂ is 85%. Literature Japanese Patent JP Zhao 53-50109 discloses a method for the manufacture of ethylamines. In this document, crude acetonitrile containing hydrocyanic acid is used as a raw material, in the presence of an organic solvent, with skeletal nickel as a catalyst, hydrogenation reaction is carried out at a hydrogen partial pressure of 0.5-10.0 MPa and a temperature of 40-200 °C to form Ethylamine, wherein the organic solvents are ethanol and toluene. After calculation, the highest yield of its ethylamine is 95.4%, which is relatively low. In addition, its reaction time is longer, and it takes three hours to complete the reaction. The catalyst consumption is relatively large, generally 12% of the acetonitrile raw material, and the catalyst activity is relatively low.

Invention content:

The purpose of the present invention is to provide a kind of reaction time is short, the catalyst of fatty nitrile liquid-phase hydrogenation of fatty primary amine of high yield of primary amine and preparation method and application.

Catalyst molar ratio of the present invention consists of:

Nickel: Cobalt: Promoter: Rare earth metal = 100: 0.01～2.0: 1～15: 0.01～1

The promoter mentioned above is one or more of chromium, iron, copper or molybdenum

Catalyst molar ratio composition preferred range is:

Nickel: cobalt: promoter: rare earth metal = 100:0.01-0.05:8-11:0.01-0.05. Catalyst preparation method of the present invention is as follows:

The soluble metal salt of the catalyst composition is prepared in proportion to a mixed aqueous solution with a concentration of 0.1-1mol/L, the temperature is raised to 60-80°C, and the molar ratio of hydrazine hydrate/metal ion = 1-5 and potassium borohydride/metal ion are added = Hydrazine hydrate and potassium borohydride co-reductant with a composition of 0.01-0.5, stirred at a constant temperature of 60-80°C for 3-5 minutes, stopped heating and stirring, washed with water until neutral, vacuum-dried and stored in absolute ethanol.

The soluble metal salts mentioned above are chlorides, sulfates or nitrates.

The application method of catalyst of the present invention is as follows:

In the present invention, when fatty nitriles are hydrogenated to produce fatty primary amines, the hydrogen pressure is between normal pressure and 5.0 MPa, the reaction temperature is 60-170°C, the solvent is ethanol, and the amount of solvent used is 0-5 times the mass of fatty nitrile raw materials, which helps The dosage of potassium carbonate is selected from 0.1% to 5% of the mass of the fatty nitrile raw material, and the dosage of the catalyst is 0.1% to 5% of the mass of the fatty nitrile raw material. The reaction temperature is more preferably in the range of 110°C to 130°C, and the hydrogen pressure is more preferably in the range of 1.0 to 2.5 MPa.

The fatty nitriles mentioned above are RCN, R-NH-CH ₂ -CH ₂ CN, RO-CH ₂ -CH ₂ CN, wherein R=C1-18.

Compared with the prior art, the present invention has the following advantages:

1. Due to the hydrogenation process of the nitrile catalyst, it undergoes the reaction process of imine. The activity of imine is very high, and it is used for further reaction with the reaction intermediate product and the main product. By-products such as secondary amine and tertiary amine are formed through condensation, aminolysis, crosslinking and other reactions, which affect the selectivity and conversion rate of the reaction. Commonly used catalysts for hydrogenation of nitriles are divided into two categories: nickel-based and cobalt-based. In general, nickel-based catalysts have high activity but low selectivity, while cobalt-based catalysts have high selectivity but low activity. The present invention greatly improves the selectivity of the nickel catalyst by introducing cobalt into the nickel catalyst, and introduces at least one component selected from Fe, Cu, Mo, and rare earth elements at the same time, so that the catalyst is compatible with its main reaction and enhances the catalyst's reaction to the nickel catalyst. The adsorption of unsaturated compounds such as imines improves the activity of the catalyst for the main reaction. High reactivity: High reactivity can be maintained under low pressure conditions. When the pressure is 1.6MPa, the reaction can be completed within 1h to 2h.

2. The reaction selectivity is high. The selectivity of primary amines produced by hydrogenation of nitrile group decreases with the decrease of carbon chain. The selectivity of the present invention to acetonitrile with the shortest carbon chain can also reach 99%.

Detailed ways

Implementation column 1:

The molar ratio is Ni: Co: Cr: La = 100: 0.01: 8: 0.03. Make the above-mentioned metal nitrate into a mixed aqueous solution with a concentration of 0.2 mol/L. After mixing evenly, heat up to 70 ° C. Under the condition of vigorous stirring Add hydrazine hydrate and potassium borohydride co-reductant in the ratio of hydrazine hydrate/metal ion=2, potassium borohydride/metal ion=0.1, react for 5 minutes, stop stirring, wash with water until neutral, vacuum dry and store in ethanol solution middle.

Using the above catalyst in a 0.5L autoclave, the reaction temperature is 110°C, the hydrogen pressure is 1.6MPa, with ethanol as the solvent, 90g of ethanol, 30g of acetonitrile, 1.5g of catalyst, and 1g of potassium carbonate as a reaction aid, at a stirring speed of 500 The reaction was performed for 60 minutes at rpm, the conversion rate of acetonitrile was 100%, and the yield of ethylamine was 96%.

Example 2

According to the molar ratio of Ni: Co: Fe: La = 100: 0.01: 11: 0.05, make the above metal sulfate into an aqueous solution with a concentration of 0.3 mol/L, mix well, heat up to 80°C, and add Hydrazine hydrate composed of hydrazine hydrate/metal ion=5, potassium borohydride/metal ion=0.04 reacted with potassium borohydride co-reductant for 4 minutes, then stopped stirring, washed with water until neutral, dried in vacuum and stored in ethanol solution .

Using the above catalyst in a 0.5L autoclave, the reaction temperature is 130°C, the hydrogen pressure is 1.8MPa, with ethanol as the solvent, 120g of ethanol, 30g of acetonitrile, 1g of catalyst, and 1.5g of potassium carbonate as a reaction aid, at a stirring speed of 500 The reaction was carried out for 70 minutes at rpm, the conversion rate of acetonitrile was 98%, and the yield of ethylamine was 97.1%.

Example 3

The molar ratio is Ni: Co: Mo: La = 100: 0.04: 9: 0.03. Make the above-mentioned metal chloride salt into an aqueous solution with a concentration of 0.5 mol/L. After mixing evenly, heat up to 65 ° C. Under the condition of vigorous stirring Add hydrazine hydrate and potassium borohydride co-reductant in the ratio of hydrazine hydrate/metal ion=3.5, potassium borohydride/metal ion=0.03, react for 5 minutes, stop stirring, wash with water until neutral, vacuum dry and store in ethanol solution middle.

Use above-mentioned catalyst in 0.5L autoclave, reaction temperature 120 ℃, hydrogen pressure 2.1MPa, take ethanol as solvent, 70g ethanol, 30g acetonitrile, 1.5g catalyst, add 0.3g potassium carbonate in addition as reaction aid, at stirring speed At 500 rpm, the reaction was carried out for 60 minutes, the conversion rate of acetonitrile was 100%, and the yield of ethylamine was 97.3%.

Example 4

The molar ratio is Ni: Co: Cu: La = 100: 0.03: 9: 0.04. Make the above metal nitrates into an aqueous solution with a concentration of 0.5 mol/L, mix well, heat up to 75°C, and add under vigorous stirring. Hydrazine hydrate composed of hydrazine hydrate/metal ion=4, potassium borohydride/metal ion=0.4 reacts with potassium borohydride co-reductant for 5 minutes, then stops stirring, washes to neutrality, vacuum-dries and stores in ethanol solution .

Use the above catalyst in a 0.5L autoclave with a reaction temperature of 120°C and a hydrogen pressure of 2.5MPa, using ethanol as a solvent, 100g of ethanol, 30g of acetonitrile, 1.5g of catalyst, and adding 1g of potassium carbonate as a reaction aid, at a stirring speed of 500 The reaction was performed for 60 minutes at rpm, the conversion rate of acetonitrile was 100%, and the yield of ethylamine was 97%.

Example 5

According to the molar ratio of Ni: Co: Cr: Mo: La = 100: 0.02: 3: 8: 0.02, make the above metal nitrate into an aqueous solution with a concentration of 0.8 mol/L, mix well and then heat up to 65°C, and stir vigorously Under certain conditions, add hydrazine hydrate and potassium borohydride co-reductant in the ratio of hydrazine hydrate/metal ion=4, potassium borohydride/metal ion=0.5, react for 3 minutes, stop stirring, wash with water until neutral, vacuum dry and store in ethanol solution.

Use above-mentioned catalyst in 0.5L autoclave, reaction temperature 120 ℃, hydrogen pressure 2.5MPa, take ethanol as solvent, 90g ethanol, 30g acetonitrile, 1.5g catalyst, add 0.15g potassium carbonate in addition as reaction auxiliary agent, stir speed is At 500 rpm, the reaction was carried out for 60 minutes, the conversion rate of acetonitrile was 100%, and the yield of ethylamine was 99.2%.

Example 6

According to the molar ratio of Ni: Co: Cr: Cu: La = 100: 0.02: 7: 1: 0.01, make the above metal nitrate into an aqueous solution with a concentration of 0.1 mol/L, mix well and then heat up to 80°C, and stir vigorously Add hydrazine hydrate/metal ion=3, potassium borohydride/metal ion=0.35 under certain conditions and react with potassium borohydride co-reductant for 5 minutes, stop stirring, wash with water until neutral, vacuum dry and store in ethanol solution.

Use above-mentioned catalyst in 0.5L autoclave, reaction temperature 120 ℃, hydrogen pressure 2.0MPa, take ethanol as solvent, 90g ethanol, 30g acetonitrile, 1.5g catalyst, add 1.2g potassium carbonate in addition as reaction auxiliary agent, stir speed is At 500 rpm, the reaction was carried out for 80 minutes, the conversion rate of acetonitrile was 100%, and the yield of ethylamine was 98.4%.

Example 7

The molar ratio is Ni: Co: Cr: Fe: La = 100: 0.02: 7: 4: 0.05. Make the above metal nitrate into an aqueous solution with a concentration of 0.4 mol/L, mix well and heat up to 70°C, and stir vigorously Under certain conditions, add hydrazine hydrate and potassium borohydride co-reductant in the ratio of hydrazine hydrate/metal ion=1, potassium borohydride/metal ion=0.03, react for 5 minutes, stop stirring, wash with water until neutral, vacuum dry and store in ethanol solution.

Use above-mentioned catalyst in 0.5L autoclave, reaction temperature 110 ℃, hydrogen pressure 1.0MPa, take ethanol as solvent, 150g ethanol, 30g acetonitrile, 1.5g catalyst, add 0.35g potassium carbonate in addition as reaction aid, at stirring speed At 500 rpm, the reaction was carried out for 160 minutes, the conversion rate of acetonitrile was 100%, and the yield of ethylamine was 98.8%.

Example 8

The molar ratio is Ni: Co: Cu: Fe: La = 100: 0.02: 8: 1: 0.03. Make the above metal nitrate into an aqueous solution with a concentration of 0.7 mol/L. Under certain conditions, add hydrazine hydrate and potassium borohydride co-reductant in the ratio of hydrazine hydrate/metal ion=1, potassium borohydride/metal ion=0.5, react for 5 minutes, stop stirring, wash with water until neutral, vacuum dry and store in ethanol solution.

Use above-mentioned catalyst in 0.5L autoclave, reaction temperature 120 ℃, hydrogen pressure 2.0MPa, take ethanol as solvent, 90g ethanol, 30g acetonitrile, 1.5g catalyst, add 0.15g potassium carbonate in addition as reaction auxiliary agent, stir speed is At 500 rpm, the reaction was carried out for 60 minutes, the conversion rate of acetonitrile was 98%, and the yield of ethylamine was 96%.

Example 9

The molar ratio is Ni: Co: Mo: Fe: La = 100: 0.02: 7: 2: 0.03. Make the above metal nitrate into an aqueous solution with a concentration of 0.7 mol/L, mix well and heat up to 70°C, and stir vigorously Add hydrazine hydrate/metal ion=3, potassium borohydride/metal ion=0.05 under the condition of hydrazine hydrate and potassium borohydride co-reductant to react for 5 minutes, stop stirring, wash with water until neutral, vacuum dry and store in ethanol solution.

Use above-mentioned catalyst in 0.5L autoclave, reaction temperature 120 ℃, hydrogen pressure 2.4MPa, take ethanol as solvent, 100g ethanol, 30g acetonitrile, 1.5g catalyst, add 0.6g potassium carbonate in addition as reaction auxiliary agent, stir speed is At 500 rpm, the reaction was carried out for 60 minutes, the conversion rate of acetonitrile was 100%, and the yield of ethylamine was 99.2%.

Example 10

The molar ratio is Ni: Co: Mo: Cu: La = 100: 0.05: 3: 6: 0.02. Make the above-mentioned metal nitrate into an aqueous solution with a concentration of 1 mol/L, mix it uniformly, and heat up to 60°C. Under the conditions, add hydrazine hydrate and potassium borohydride co-reductant in the ratio of hydrazine hydrate/metal ion=5, potassium borohydride/metal ion=0.01, react for 5 minutes, stop stirring, wash with water until neutral, vacuum dry and store in in ethanol solution.

Use above-mentioned catalyzer in 0.5L autoclave, reaction temperature 120 ℃, hydrogen pressure 1.9MPa, take ethanol as solvent, 60g ethanol, 30g acetonitrile, 1.5g catalyst, add 1.3g potassium carbonate in addition as reaction auxiliary agent, stir speed is At 500 rpm, the reaction was carried out for 60 minutes, the conversion rate of acetonitrile was 100%, and the yield of ethylamine was 97%.

Example 11

According to the molar ratio of Ni: Co: Mo: Cu: Ce = 100: 0.02: 2: 9: 0.04, make the above metal nitrate into an aqueous solution with a concentration of 0.35 mol/L, mix well and heat up to 75 ° C, and stir vigorously Under certain conditions, add hydrazine hydrate and potassium borohydride co-reductant in the ratio of hydrazine hydrate/metal ion=4, potassium borohydride/metal ion=0.42, react for 5 minutes, stop stirring, wash with water until neutral, vacuum dry and store in ethanol solution.

Using the above-mentioned catalyst in a 0.5L autoclave, the reaction temperature is 120°C, the hydrogen pressure is 2.1MPa, 100g of octadecanonitrile, 1.0g of catalyst, and 4g of potassium carbonate is added as a reaction aid. At a stirring speed of 500 rpm, the reaction After 110 minutes, the conversion rate of octadecanonitrile was 100%, and the yield of octadecylamine was 99.4%.

Example 12

According to the molar ratio of Ni: Co: Mo: Fe: Cu: Sm = 100: 0.02: 3: 3: 4: 0.02, make the above metal nitrate into an aqueous solution with a concentration of 0.25 mol/L, mix well and heat up to 80°C , add hydrazine hydrate and potassium borohydride co-reductant in the ratio of hydrazine hydrate/metal ion=3, potassium borohydride/metal ion=0.35 and react for 5 minutes, then stop stirring, wash with water until neutral, pump Store in ethanol solution after vacuum drying.

Using the above catalyst in a 0.5L autoclave, the reaction temperature is 110°C, the hydrogen pressure is 1.8MPa, 100g hexadecanonitrile, 1.0g catalyst, and 3g potassium carbonate is added as a reaction aid, and the reaction is carried out at a stirring speed of 500 rpm. After 90 minutes, the conversion rate of hexadecanonitrile was 100%, and the yield of hexadecylamine was 99.1%.

Example 13

The molar ratio is Ni: Co: Cr: Fe: Mo: Cu: Sm = 100: 0.01: 3: 4: 2: 1: 0.01. Make the above-mentioned metal nitrate into an aqueous solution with a concentration of 0.8 mol/L, and mix it evenly Raise the temperature to 80°C, add hydrazine hydrate and potassium borohydride co-reducing agent in the ratio of hydrazine hydrate/metal ion=2, potassium borohydride/metal ion=0.5 and react for 5 minutes, then stop stirring and wash with water until Neutral, vacuum dried and stored in ethanol solution.

Use above-mentioned catalyst in 0.5L autoclave, reaction temperature 130 ℃, hydrogen pressure 2.5MPa, 100g3-octadecylpropionitrile, 1.0g catalyst, add 5g potassium carbonate in addition as reaction auxiliary agent, at stirring speed be 500 rpm After 80 minutes of reaction, the conversion rate of 3-octadecylpropionitrile was 100%, and the yield of N-octadecyl-1,3-propylenediamine was 99%.

Example 14

The molar ratio is Ni: Co: Cu: La = 100: 0.05: 10: 0.02. Make the above metal nitrate into an aqueous solution with a concentration of 0.5 mol/L, mix well, heat up to 75°C, and add under vigorous stirring. Hydrazine hydrate composed of hydrazine hydrate/metal ion=3.5, potassium borohydride/metal ion=0.45 reacts with potassium borohydride co-reductant for 5 minutes, stops stirring, washes to neutrality, vacuum-dries and stores in ethanol solution .

Using the above catalyst in a 0.5L autoclave, the reaction temperature is 110°C, the hydrogen pressure is 2.0MPa, 100g 3-isotridecyloxypropionitrile, 1.0g catalyst, and 1.5g potassium carbonate is added as a reaction aid. At 500 r/min, the reaction was carried out for 90 minutes, the conversion rate of 3-isotridecyloxypropionitrile was 100%, and the yield of 3-isotridecyloxypropylamine was 99.2%.

Claims (7)

1. A catalyst for the hydrogenation of fatty nitriles to produce primary fatty amines, characterized in that the molar ratio of the catalyst consists of: Nickel: cobalt: promoter: rare earth metal = 100: 0.01～2.0: 1～15: 0.01～1 The promoter mentioned above is one or more of chromium, iron, copper or molybdenum 2. A catalyst for preparing fatty primary amines by hydrogenation of fatty nitriles as claimed in claim 1, characterized in that the molar ratio of the catalyst is composed of: Nickel: cobalt: promoter: rare earth metal = 100:0.01-0.05:8-11:0.01-0.05. 3. The preparation method of a catalyst for hydrogenating fatty nitriles to produce fatty primary amines as claimed in claim 1 or 2, characterized in that it comprises the following steps: The soluble metal salt of the catalyst composition is prepared in proportion to a mixed aqueous solution with a concentration of 0.1-1mol/L, the temperature is raised to 60-80°C, and the molar ratio of hydrazine hydrate/metal ion = 1-5 and potassium borohydride/metal ion are added = Hydrazine hydrate and potassium borohydride co-reductant with a composition of 0.01-0.5, stirred at a constant temperature of 60-80°C for 3-5 minutes, stopped heating and stirring, washed with water until neutral, vacuum-dried and stored in absolute ethanol. 4. The preparation method of a catalyst for hydrogenating fatty nitriles to fatty primary amines as claimed in claim 3, characterized in that said soluble metal salts are chlorides, sulfates or nitrates. 5. The application method of a catalyst for hydrogenating fatty nitriles to produce fatty primary amines as claimed in claim 1 or 2, characterized in that it comprises the following steps: When fatty nitrile is hydrogenated to produce fatty primary amine, the hydrogen pressure is between normal pressure and 5.0MPa, the reaction temperature is 60-170°C, the solvent is ethanol, and the amount of solvent is 0-5 times the mass of fatty nitrile raw material, and the auxiliary agent is selected from The dosage of potassium carbonate is 0.1%-5% of the mass of the fatty nitrile raw material, and the dosage of the catalyst is 0.1%-5% of the mass of the fatty nitrile raw material. 6. The application method of a catalyst for producing fatty primary amines by hydrogenation of fatty nitriles as claimed in claim 5, characterized in that the reaction temperature is 110°C-130°C, and the hydrogen pressure is 1.0-2.5MPa. 7. The application method of a catalyst for the hydrogenation of fatty nitriles to fatty primary amines as claimed in claim 5, characterized in that the fatty nitriles are RCN, R-NH-CH ₂ -CH ₂ CN, RO-CH ₂ -CH ₂ CN, wherein R=C1-18.