A hydrogenation catalyst, a preparation method and application thereof, and a preparation method of 1,4-butanediamine

Abstract

The application provides a hydrogenation catalyst and a preparation method and application thereof, and a preparation method of 1,4-butanediamine, and relates to the technical field of organic synthesis. The preparation method of the hydrogenation catalyst provided by the application comprises the following steps: mixing a metal salt and water to obtain an active component aqueous solution; the metal salt comprises one or more of a magnesium salt, an aluminum salt and a nickel salt; mixing the active component aqueous solution and gamma-Al2O3, and sequentially performing rotary evaporation and drying to obtain a catalyst precursor; and sequentially performing shaping and calcination on the catalyst precursor to obtain the hydrogenation catalyst. The hydrogenation catalyst prepared by the application can be used for preparing 1,4-butanediamine by hydrogenating 4-aminobutyronitrile.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, in particular to a hydrogenation catalyst, a preparation method and application thereof, and a preparation method of 1,4-butanediamine. BACKGROUND

[0002] High-temperature nylon refers to nylon materials that can be used in an environment above 150 DEG C for a long time, with a melting point generally between 290 DEG C and 320 DEG C, and excellent mechanical properties in a wide temperature range and high humidity environment. Currently, the mature industrialized high-temperature nylon varieties include nylon 46, nylon 4T, nylon 6T, etc. From a broad classification, they can be classified into aliphatic nylon, semi-aromatic nylon, fully aromatic nylon and alicyclic nylon. The most representative one in the aliphatic nylon is nylon 46.

[0003] The relative molecular mass of nylon 46 can reach about 3000, and the Dutch DSM company calls it "super nylon". Its characteristics are high-temperature resistance, a melting point of 295 DEG C, which is 40 DEG C higher than that of nylon 66 and 80 DEG C higher than that of nylon 6, and a long-term use temperature of 163 DEG C. Although nylon 46 has a similar molecular structure to nylon 6 and nylon 66, the number of amide groups on the chain of a given length of nylon 46 is more, and the chain structure is more symmetrical. The highly symmetrical chain structure results in high crystallinity, and the crystallization speed is 4-5 times that of nylon 66 and 10 times that of nylon 6. These characteristics make nylon 46 have technical advantages in mechanical strength, wear resistance and other aspects under heat resistance and high temperature compared with other engineering plastics such as nylon 6 and nylon 66. Therefore, nylon 46 has broad application prospects.

[0004] Nylon 46 is obtained by polycondensation of 1,4-butanediamine and adipic acid, and 1,4-butanediamine is synthesized by hydrogenation of succinonitrile. Succinonitrile is the main raw material for producing nylon 46. The DSM company uses acrylonitrile and hydrogen cyanide as raw materials to produce succinonitrile, and this technology needs to be broken through. SUMMARY

[0005] The present application provides a hydrogenation catalyst, a preparation method and application thereof, and a preparation method of 1,4-butanediamine.

[0006] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0007] The present application provides a preparation method of a hydrogenation catalyst, comprising the following steps:

[0008] Mixing a metal salt and water to obtain an active component aqueous solution; the metal salt includes one or more of a magnesium salt, an aluminum salt and a nickel salt;

[0009] Mixing the active component aqueous solution and γ-Al2O3, and sequentially performing rotary evaporation and drying to obtain a catalyst precursor;

[0010] Forming and calcining the catalyst precursor to obtain a hydrogenation catalyst.

[0011] Preferably, the mass fraction of the magnesium salt in the active component aqueous solution is 0-30%; the mass fraction of the aluminum salt is 0-45%; the mass fraction of the nickel salt is 0-30%; the mass fractions of the magnesium salt, the aluminum salt and the nickel salt in the active component aqueous solution are not all 0.

[0012] Preferably, the magnesium salt comprises one or more of magnesium nitrate and magnesium phosphate;

[0013] The aluminum salt comprises one or more of aluminum nitrate and aluminum phosphate;

[0014] The nickel salt comprises one or more of nickel nitrate and nickel chloride.

[0015] Preferably, the temperature of the rotary evaporation is 20-90℃; the time of the rotary evaporation is 0.5-4h.

[0016] Preferably, the temperature of the drying is 30-120℃; the time of the drying is 1-5h.

[0017] Preferably, the temperature of the calcination is 100-550℃; the time of the calcination is 1-6h; the calcination is performed in a protective atmosphere.

[0018] The application provides a hydrogenation catalyst prepared by the preparation method, comprising γ-Al2O3 and metal oxides supported on the γ-Al2O3; the metal oxides comprise one or more of magnesium oxide, aluminum oxide and nickel oxide.

[0019] The application provides an application of the hydrogenation catalyst in a 4-aminobutyronitrile hydrogenation reaction.

[0020] The application provides a preparation method of 1,4-diaminobutane, comprising the following steps:

[0021] Mixing 4-aminobutyronitrile and a hydrogenation catalyst, and performing a hydrogenation reaction in a hydrogen atmosphere to obtain 1,4-diaminobutane; the hydrogenation catalyst is the hydrogenation catalyst described in the above technical solution.

[0022] Preferably, the temperature of the hydrogenation reaction is 50-95℃.

[0023] This invention provides a method for preparing a hydrogenation catalyst. Using γ-Al₂O₃ as a support, one or more active components selected from magnesium oxide, aluminum oxide, and nickel oxide are loaded onto the γ-Al₂O₃. The prepared hydrogenation catalyst can be used for the hydrogenation of 4-aminobutyronitrile to 1,4-butanediamine. Example results show that using the hydrogenation catalyst provided by this invention for the hydrogenation of 4-aminobutyronitrile can achieve a selectivity of greater than 30% for the product 1,4-butanediamine.

[0024] In addition, the preparation method provided by this invention is simple and suitable for widespread application. Detailed Implementation

[0025] This invention provides a method for preparing a hydrogenation catalyst, comprising the following steps:

[0026] A metal salt is mixed with water to obtain an aqueous solution of the active component; the metal salt includes one or more of magnesium salts, aluminum salts, and nickel salts;

[0027] The aqueous solution of the active component and γ-Al2O3 were mixed and then subjected to rotary evaporation and drying to obtain the catalyst precursor.

[0028] The catalyst precursor was sequentially shaped and calcined to obtain the hydrogenation catalyst.

[0029] This invention involves mixing a metal salt with water to obtain an aqueous solution of the active component. In this invention, the metal salt includes one or more of magnesium, aluminum, and nickel salts. Preferably, the mass fraction of magnesium salt in the aqueous solution of the active component is 0-30%, more preferably 3.5-20%; the mass fraction of aluminum salt is preferably 0-45%, more preferably 3.5-35%; and the mass fraction of nickel salt is preferably 0-30%, more preferably 2.1-20%. The mass fractions of magnesium, aluminum, and nickel salts in the aqueous solution of the active component are not simultaneously 0.

[0030] In this invention, the magnesium salt preferably includes one or more of magnesium nitrate and magnesium phosphate; the aluminum salt preferably includes one or more of aluminum nitrate and aluminum phosphate; and the nickel salt preferably includes one or more of nickel nitrate and nickel chloride.

[0031] After obtaining the aqueous solution of the active component, the present invention mixes the aqueous solution of the active component with γ-Al2O3, and sequentially performs rotary evaporation and drying to obtain the catalyst precursor. The present invention does not have special requirements for the γ-Al2O3; commercially available products well known to those skilled in the art can be used.

[0032] In this invention, the mass ratio of the active component aqueous solution to γ-Al2O3 is preferably 140-300:50-150, more preferably 143:100.

[0033] In this invention, the temperature of the rotary evaporation is preferably 20-90°C, more preferably 60-85°C; the time of the rotary evaporation is preferably 0.5-4 hours, more preferably 1-2 hours.

[0034] In this invention, the drying temperature is preferably 30-120°C, more preferably 90-100°C; the drying time is preferably 1-5 hours, more preferably 2-4 hours.

[0035] After obtaining the catalyst precursor, the present invention sequentially shapes and calcines the catalyst precursor to obtain a hydrogenation catalyst. In the present invention, the shaping method preferably includes compression molding. The present invention does not have special requirements for the specific process of compression molding; compression molding processes well known to those skilled in the art can be used.

[0036] In this invention, the calcination temperature is preferably 100–550°C, more preferably 200–500°C; the calcination time is preferably 1–6 hours, more preferably 2–4 hours. In this invention, the calcination is preferably carried out in a protective atmosphere, more preferably in a nitrogen atmosphere.

[0037] In the roasting process of the present invention, the metal salt decomposes into metal oxide, and the metal oxide is loaded onto γ-Al2O3 as an active component.

[0038] In this invention, the hydrogenation catalyst is in the form of a powder.

[0039] The present invention provides a hydrogenation catalyst prepared by the preparation method described above, comprising γ-Al2O3 and a metal oxide supported on the γ-Al2O3; the metal oxide comprises one or more of magnesium oxide, aluminum oxide and nickel oxide.

[0040] This invention provides the application of the hydrogenation catalyst described in the above technical solution in the hydrogenation reaction of 4-aminobutyronitrile.

[0041] This invention provides a method for preparing 1,4-butanediamine, comprising the following steps:

[0042] 4-Aminobutyronitrile and a hydrogenation catalyst are mixed and hydrogenated in a hydrogen atmosphere to obtain 1,4-butanediamine; the hydrogenation catalyst is the hydrogenation catalyst described in the above technical solution.

[0043] In this invention, the mass ratio of the 4-aminobutyronitrile to the hydrogenation catalyst is preferably 30-100:0.1-5, more preferably 50-80:2-4.

[0044] In this invention, the method for providing the hydrogen atmosphere includes: introducing high-purity nitrogen into the autoclave three times for purging, and then introducing high-purity hydrogen into the autoclave three times for purging, with a purging pressure of 0.1 to 2 MPa.

[0045] In this invention, the temperature of the hydrogenation reaction is preferably 50–95°C, more preferably 60–75°C. The pressure of the hydrogenation reaction is preferably 0.1–3.0 MPa, more preferably 1.0–3.0 MPa. The time of the hydrogenation reaction is preferably 0.5–4 h, more preferably 1–3 h. The hydrogenation reaction is preferably carried out under stirring conditions; the stirring rate is preferably 20–200 rpm, more preferably 50–150 rpm. The hydrogenation reaction is preferably carried out under ammonia-free conditions.

[0046] In this invention, the heating rate from room temperature to the temperature of the hydrogenation reaction is preferably 10 to 30 °C / min, more preferably 20 °C / min.

[0047] In this invention, the selectivity of the 1,4-butanediamine is greater than 30%. In this invention, the hydrogenation reaction of 4-aminobutyronitrile is most effective under ammonia-free conditions.

[0048] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0049] Example 1

[0050] Mix 5g magnesium nitrate, 5g aluminum nitrate, 3g nickel nitrate and 130g water to obtain an aqueous solution of the active component;

[0051] 100g of γ-Al2O3 was placed in a rotary evaporator, and the aqueous solution of the active component was added to the γ-Al2O3. The rotary evaporator was heated to 60°C and rotated for 4 hours. The water was then removed by vacuuming. The resulting solid material was dried at 120°C for 3 hours, pressed into shape, and then calcined at 550°C for 4 hours under a nitrogen atmosphere to obtain the hydrogenation catalyst.

[0052] Application Example 1

[0053] 50g of 4-aminobutyronitrile and 2g of the hydrogenation catalyst prepared in Example 1 were added to a miniature high-pressure reactor with a polytetrafluoroethylene liner. The high-pressure reactor was sealed, and after checking the airtightness, high-purity nitrogen was introduced into the high-pressure reactor three times for purging, followed by high-purity hydrogen three times for purging, with a purging pressure of 2MPa. The high-pressure reactor was heated at a heating rate of 20℃ / min to 75℃, and hydrogen was introduced to pressurize to the reaction pressure of 3.0MPa. The stirring device was started, and the stirring speed was 100rpm to carry out the hydrogenation reaction for 0.5h.

[0054] After the hydrogenation reaction is completed, the temperature controller and stirring device are turned off. After the temperature of the autoclave drops to room temperature, the pressure is released, and the resulting reaction system is allowed to stand and separate into layers. The hydrogenation catalyst is removed by filtration to obtain the product. The content of 1,4-butanediamine in the product is analyzed by gas chromatography.

[0055] Analysis showed that the selectivity of 1,4-butanediamine in the product was 32%.

[0056] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. The application of a hydrogenation catalyst in the hydrogenation of 4-aminobutyronitrile to prepare 1,4-butanediamine, characterized in that, The hydrogenation catalyst comprises γ-Al₂O₃ and a metal oxide supported on the γ-Al₂O₃; the metal oxide is composed of magnesium oxide, aluminum oxide and nickel oxide. The preparation method of the hydrogenation catalyst includes the following steps: A metal salt is mixed with water to obtain an aqueous solution of the active component; the metal salt is composed of magnesium salt, aluminum salt and nickel salt. The aqueous solution of the active component and γ-Al2O3 were mixed and then subjected to rotary evaporation and drying to obtain the catalyst precursor. The catalyst precursor was sequentially shaped and calcined to obtain a hydrogenation catalyst. The active ingredient aqueous solution contains 3.5-20% magnesium salt, 3.5-35% aluminum salt, and 2.1-20% nickel salt by mass. The rotary evaporation temperature is 20~90℃; the rotary evaporation time is 0.5~4h.

2. The application according to claim 1, characterized in that, The magnesium salt includes magnesium nitrate; The aluminum salt includes aluminum nitrate; The nickel salt includes one or more of nickel nitrate and nickel chloride.

3. The application according to claim 1, characterized in that, The drying temperature is 30~120℃; the drying time is 1~5h.

4. The application according to claim 1, characterized in that, The roasting temperature is 100~550℃; the roasting time is 1~6h; the roasting is carried out in a protective atmosphere.

5. A method for preparing 1,4-butanediamine, characterized in that, Includes the following steps: 4-Aminobutyronitrile and a hydrogenation catalyst are mixed and hydrogenated in a hydrogen atmosphere to obtain 1,4-butanediamine; the hydrogenation catalyst comprises γ-Al2O3 and a metal oxide supported on the γ-Al2O3; the metal oxide is composed of magnesium oxide, aluminum oxide and nickel oxide. The preparation method of the hydrogenation catalyst includes the following steps: A metal salt is mixed with water to obtain an aqueous solution of the active component; the metal salt is composed of magnesium salt, aluminum salt and nickel salt. The aqueous solution of the active component and γ-Al2O3 were mixed and then subjected to rotary evaporation and drying to obtain the catalyst precursor. The catalyst precursor was sequentially shaped and calcined to obtain a hydrogenation catalyst. The active ingredient aqueous solution contains 3.5-20% magnesium salt, 3.5-35% aluminum salt, and 2.1-20% nickel salt by mass. The rotary evaporation temperature is 20~90℃; the rotary evaporation time is 0.5~4h.

6. The preparation method according to claim 5, characterized in that, The hydrogenation reaction is carried out at a temperature of 50~95℃.