CN112898163B

CN112898163B - Method for preparing 1, 6-hexamethylene diamine by ammoniation of hexamethylene imine

Info

Publication number: CN112898163B
Application number: CN201911220696.8A
Authority: CN
Inventors: 马雷; 丁云杰; 严丽; 程显波
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2019-12-03
Filing date: 2019-12-03
Publication date: 2022-06-24
Anticipated expiration: 2039-12-03
Also published as: CN112898163A

Abstract

The invention relates to a method for preparing 1, 6-hexamethylene diamine by aminating hexamethylene imine. The catalyst in the method comprises three parts of an active component, an auxiliary agent and a carrier: the active component is one or the combination of transition metals Ni, Fe, Ru and Re, the auxiliary agent is one or the combination of elements W, B, Ir, Pt, Os, Co, Cu, Rh and Mo, and the carrier is selected from ammoniated Al₂O₃Active carbon, molecular sieve and SiO_2、Al₂O₃‑SiO₂One or a combination of (a). The weight of the active component in the catalyst accounts for 1-45% of the weight of the catalyst, and the weight of the auxiliary agent accounts for 0.05-15% of the weight of the catalyst. The catalyst is used for preparing 1, 6-hexamethylene diamine by ammonifying cyclohexane under hydrogen atmosphere, and has the advantages of high activity, high yield of target products, good stability, good economy and the like, and has wide application prospect.

Description

Method for preparing 1, 6-hexamethylene diamine by ammoniation of hexamethylene imine

Technical Field

The invention relates to a method for preparing 1, 6-hexamethylene diamine by ammoniation of hexamethylene imine, in particular to a catalyst for catalyzing the ammoniation reaction of the hexamethylene imine and ammonia to generate the 1, 6-hexamethylene diamine under a hydrogen atmosphere.

Background

1, 6-hexamethylene diamine is used as an important organic amine product and is widely applied to the fields of producing polyhexamethylene adipamide (nylon 66), hexamethylene isocyanate, synthetic resin, organic cross-linking agents and the like. With the rapid development of the synthetic material industry at home and abroad, the demand of 1, 6-hexamethylene diamine is increasing day by day, so that the research and development of a novel catalyst for synthesizing the 1, 6-hexamethylene diamine has wide market prospect.

The production process of the common 1, 6-hexamethylene diamine mainly comprises the following steps: 1, 6-adiponitrile hydrogenation, amination with 1, 6-hexanediol or 6-amino-1-hexanol, caprolactam, reductive amination with 1, 6-hexanedial, and the like. The main process for preparing 1, 6-hexanediamine at present is to use butadiene as a raw material and perform hydrocyanation reaction to generate 1, 6-adiponitrile, and then perform hydrogenation on the 1, 6-adiponitrile. The process has great technical difficulty and is monopolized by foreign chemical industry for a long time. In addition, the process also faces various problems of high energy consumption, complex process route, virulent raw material hydrocyanic acid and the like. Other 1, 6-hexanediamine production processes also suffer from one or more problems of immature technology, high raw material cost, low 1, 6-hexanediamine yield, complex product distribution and the like. Therefore, it is urgently needed to develop a process route with good economy, simple technology and easy operation.

The cycloheximide, also known as hexamethyleneimine or homopiperidine, is used as a fine chemical intermediate and widely applied in the fields of medicines, pesticides, catalyst templates and the like. However, the market demand for cycloheximide is small at present, which results in the demand for products being larger than the demand. In addition, cycloheximide is a main byproduct in the industrial production process of 1, 6-hexamethylenediamine, which results in the reduction of the yield of 1, 6-hexamethylenediamine on the one hand and the waste of resources caused by the stockpiled cycloheximide in the factory on the other hand. The method for preparing the 1, 6-hexamethylene diamine by taking the cycloheximide and the ammonia as raw materials through an ammoniation reaction is the most effective method for improving the added value of products and solving the problems, but the research reports about the reaction are less at present.

In the U.S. Pat. No. 2166151, metal Ni is used as a catalyst for the hydrogenation of 1, 6-adiponitrile to prepare 1, 6-hexamethylenediamine, the reaction is carried out in an autoclave, and the selectivity of the product hexamethylenediamine is over 80 percent. Chinese patent 109647419 Ni/Al modified by rare earth metal oxide₂O₃The catalyst is used for hydrogenation reaction of 1, 6-adiponitrile, the conversion rate is close to 100%, and the selectivity of hexamethylene diamine in the product can reach 90%. U.S. Pat. No. 2657239 discloses the use of Raney Ni in the reductive amination of 1, 6-hexanedial to 1, 6-hexanediamine, with a selectivity ratio of 1, 6-hexanediamine to cyclohexylimine of about 2: 1. U.S. Pat. No. 2754330 discloses a charcoal-supported Ru-based catalyst for the catalytic amination of 1, 6-hexanediol to produce 1, 6-hexamethylenediamine in about 25% yield. U.S. Pat. No. 3270059 uses activated Co powder as catalyst for amination of 1, 6-hexanediol, the reaction is carried out in an autoclave, and the selectivity of 1, 6-hexanediol in the product is about 35%. Chinese patent 104262168 discloses a process for further producing 1, 6-hexanediamine from cyclohexene via 1, 6-hexanedialdehydeRoute using Ni/Al₂O₃-SiO₂The purity of the 1, 6-hexamethylene diamine can reach more than 99 percent after the product of the catalyst is rectified and purified. Chinese patents 106807377 and 106807395 report a novel supported catalyst for amination of 1, 6-hexanediol, wherein the catalyst takes Ni or Co as a main active component, Cu, Re, B and the like as auxiliaries and SiO₂、Al₂O₃And (4) ammoniating the carrier. The reaction is carried out in a fixed bed reactor at 160 ℃ and 8MPa, and the conversion rate of 1, 6-hexanediol and the selectivity of 1, 6-hexamethylenediamine can respectively reach 95.05 percent and 86.61 percent.

The patent of synthesizing 1, 6-hexamethylene diamine by using cycloheximide as raw material has less reports, and U.S. Pat. No. 3268588 reports that a Raney Ni catalyst can promote the conversion of cycloheximide to 1, 6-hexamethylene diamine, and the reaction yield is about 50%. In the U.S. Pat. No. 3270059, cyclohexylimine and liquid ammonia are used as raw materials to react to produce 1, 6-hexanediamine in a Co catalyst in a kettle reactor, the conversion rate is about 38%, and the selectivity of 1, 6-hexanediamine in the product is about 28%.

As can be seen from the above review, the amination of cyclohexylimine to 1, 6-hexamethylenediamine according to the prior art has one or more problems of low catalyst activity, low product yield, inability to achieve continuous production, poor stability, etc.

Disclosure of Invention

The application aims to provide a method for preparing 1, 6-hexamethylene diamine by ammonifying cyclohexylimine, wherein a catalyst in the method has the advantages of simple preparation process and easiness in operation, and the catalyst has the characteristics of high catalytic activity, high yield of 1, 6-hexamethylene diamine, adjustable product distribution, good stability, green and clean reaction process and the like when being used for the ammonification reaction of cyclohexylimine.

According to one aspect of the application, the application provides a method for preparing 1, 6-hexamethylene diamine by aminating hexamethylene imine, wherein a catalyst in the method consists of an active component, an auxiliary agent and a carrier, wherein the active component is one or a combination of more than two of transition metal elements of Ni, Fe, Ru and Re; the auxiliary agent is one or the combination of more than two of elements of W, B, Ir, Pt, Os, Co, Cu, Rh and Mo; the carrier is selected fromAmmoniated Al₂O₃Active carbon, molecular sieve and SiO₂、Al₂O₃-SiO₂One or a combination of two or more of (1).

In a preferred embodiment, the carrier is aminated.

In another preferred embodiment, the weight of the active component accounts for 1-45% of the weight of the catalyst;

in another preferred embodiment, the weight of the auxiliary agent accounts for 0.05-15% of the weight of the catalyst;

in another preferred embodiment, the specific surface area of the carrier is 50 to 1800m²The pore volume is 0.2-1.2 ml/g.

More specifically, the application provides a method for preparing 1, 6-hexamethylene diamine by aminating hexamethylene imine, wherein a catalyst in the method is a supported catalyst, and the catalyst comprises an active component, an auxiliary agent and a carrier.

The active component of the catalyst is transition metal element, and the transition metal element is one or the combination of more than two of Ni, Fe, Ru and Re.

The catalyst auxiliary agent is an auxiliary agent element, and the auxiliary agent element is one or a combination of more than two of W, B, Ir, Pt, Os, Co, Cu, Rh and Mo. Preferably, the auxiliary element is one or a combination of more than two of W, Os, Co, Rh and Mo.

The auxiliary agent comprises the auxiliary agent element and/or an oxide of the auxiliary agent element.

The carrier is selected from Al subjected to ammoniation treatment₂O₃Active carbon, molecular sieve and SiO₂、Al₂O₃-SiO₂One or a combination of two or more of (1). Preferably, the support is selected from the group consisting of ammoniated Al₂O₃Activated carbon, SiO₂One or a combination of two or more of (1).

The carrier is subjected to ammoniation treatment, and is characterized in that the carrier is contacted with an ammonia source at the temperature of 100-500 ℃ for 0.5-10 h.

The ammonia source comprises one of ammonia gas, ammonia water with the mass concentration of 5-28%, liquid ammonia and carbamide. Preferably, the source of ammonia is selected from ammonia gas.

The weight of the active component in the catalyst accounts for 1-45% of the weight of the catalyst. Preferably, the weight of the active component accounts for 5-25% of the weight of the catalyst.

The weight of the auxiliary agent in the catalyst accounts for 0.05-15% of the weight of the catalyst. Preferably, the weight of the auxiliary agent accounts for 0.5-8% of the weight of the catalyst

The specific surface area of the carrier in the catalyst is 50-1800 m²The pore volume is 0.2-1.2 ml/g. Preferably, the specific surface area of the carrier is 300-1200 m²The pore volume is 0.3-0.8 ml/g.

According to another aspect of the application, a preparation method of the catalyst is provided, and the method is simple, convenient, easy to operate and suitable for large-scale production.

The preparation method of the catalyst is characterized in that the catalyst adopts an impregnation method and/or a precipitation method to load the active component and the auxiliary agent on the carrier after ammoniation treatment.

The carrier ammonification treatment process is characterized in that the carrier is contacted with an ammonia source for 0.5-10 hours at the temperature of 100-500 ℃.

The ammonia source is selected from one of ammonia gas, ammonia water, liquid ammonia and carbamide.

Optionally, the carrier ammonification process comprises the following steps:

weighing a certain amount of carrier, placing the carrier in a tube furnace, introducing ammonia gas, adjusting the temperature to be within the range of 100-500 ℃, and treating for 0.5-10 h.

Optionally, the impregnation method comprises the steps of:

and (3) soaking the ammoniated carrier in an aqueous solution containing an active component precursor and an auxiliary agent precursor, naturally airing, and roasting to obtain the catalyst.

Optionally, the roasting temperature is 200-600 ℃ and the roasting time is 0.5-15 h. The roasting atmosphere is air or oxygen. When the carrier is active carbon, the roasting atmosphere is one of nitrogen, argon and helium.

Optionally, the precipitation method comprises the steps of:

adding an active component precursor and an auxiliary agent precursor into a suspension containing an aminated carrier, adding a precipitator, and aging, washing, filtering, drying and roasting to obtain the catalyst.

Optionally, the active component precursor comprises a soluble salt of Ni, a soluble salt of Fe, a soluble compound of Ru, a soluble salt of Re.

Optionally, the promoter precursor comprises a soluble precursor of a promoter element.

Specifically, the soluble salt of Ni used may be nickel nitrate, nickel acetate, nickel chloride, nickel sulfate or nickel citrate, preferably nickel nitrate, nickel acetate.

The soluble salt of Fe can be ferric chloride, ferric nitrate, ferrous chloride, and ferrous sulfate, preferably ferrous nitrate.

The soluble compound of Ru may be ruthenium chloride, ruthenium iodide, ruthenium acetate, potassium chlororuthenate, sodium chlororuthenate, ammonium chlororuthenate, ruthenium carbonyl chloride, ruthenium triphenylphosphine chloride, ruthenium p-cymene dichloride, preferably ruthenium chloride, ruthenium acetate.

The soluble salt of Re used is ammonium rhenate, perrhenic acid or rhenium chloride, preferably ammonium rhenate.

The soluble salt of the metal auxiliary agent is nitrate or chloride.

The nonmetal auxiliary agent B is boric acid.

Alternatively, the preparation method of the catalyst can adopt one or two of an impregnation method and a precipitation method to load the active component and the auxiliary agent on the ammoniated carrier.

In a preferred embodiment, the active ingredient and the auxiliary agent can be supported on the aminated support material by impregnation.

Alternatively, in the impregnation method embodiment, the active ingredient and the auxiliary agent may be supported on the aminated support by co-impregnation or stepwise impregnation.

Alternatively, the impregnation method may include the steps of: preparing an aqueous solution containing an active component and an auxiliary agent precursor, wherein the weight of the active component accounts for 1-45% of the weight of the catalyst, the weight of the auxiliary agent accounts for 0.05-15% of the weight of the catalyst, impregnating the aqueous solution containing the active component and the auxiliary agent into the ammoniated carrier, and naturally airing and roasting the carrier.

Alternatively, the impregnation method may be one-time impregnation or multi-stage impregnation.

Optionally, the roasting temperature is usually 200-600 ℃ and the roasting time is 0.5-15 h. The roasting atmosphere is air or oxygen. When the carrier is active carbon, the roasting atmosphere is one of nitrogen, argon and helium.

Alternatively, the catalyst precursor may also be supported on a carrier by a precipitation method.

Alternatively, the step of preparing the catalyst by the precipitation method can be as follows: the ammoniated carrier material is suspended in water, and soluble precursors of the active ingredient and the adjuvant, such as metal salts, are added, followed by the addition of a precipitating agent to precipitate the active ingredient and adjuvant onto the suspended carrier. Wherein the weight of the active component accounts for 1-45% of the weight of the catalyst, and the weight of the auxiliary agent accounts for 0.05-15% of the weight of the catalyst. And (4) aging, washing, filtering, drying and roasting the precipitated sample.

Alternatively, the precipitant used is preferably an inorganic base, preferably sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate.

Alternatively, the precipitant used may also be an ammonium salt, which may be ammonium carbonate, ammonium hydroxide or ammonium halide.

Optionally, the precipitation temperature may be 20 to 100 ℃, preferably 40 to 60 ℃.

The catalyst needs to be activated before being used for the ammination reaction of the cycloheximide.

The catalyst activation treatment is carried out in a hydrogen atmosphere, and the activation conditions are as follows: the temperature is 100-600 ℃, and preferably 150-500 ℃; the pressure is 0.1 MPa; the time is 0.5-10 h, preferably 1-7 h; the gas airspeed is 20-3000 h^-1Preferably 100 to 2000 hours^-1。

The hydrogen atmosphere comprises hydrogen, hydrogen and inert gas mixture, wherein the inert gas can be nitrogen, helium or argon. In the mixture of the hydrogen and the inert gas, the volume proportion of the hydrogen is 1-99%. Preferably, the hydrogen atmosphere is hydrogen.

According to another aspect of the application, a process route for preparing 1, 6-hexamethylene diamine by ammoniation with cycloheximide as a raw material is provided, and the process has one or more advantages of readily available raw materials, good economy, adjustable product distribution, high yield of 1, 6-hexamethylene diamine, simple process route and the like.

The amination takes cycloheximide and ammonia as raw materials, adopts the catalyst provided by the application, and generates an amine product taking 1, 6-hexamethylene diamine as a main product through catalytic amination reaction under a certain reaction condition in a hydrogen atmosphere.

The catalyst comprises a multi-metal active component, a carrier and an auxiliary agent. The active component is one or the combination of more than two of transition metal elements of Ni, Fe, Ru and Re; the auxiliary agent is one or the combination of more than two of elements of W, B, Ir, Pt, Os, Co, Cu, Rh and Mo; the carrier is selected from Al subjected to ammoniation treatment₂O₃Active carbon, molecular sieve and SiO₂、Al₂O₃-SiO₂One or a combination of two or more of (1).

The carrier is subjected to ammoniation treatment.

The weight of the active component accounts for 1-45% of the weight of the catalyst; the weight of the auxiliary agent accounts for 0.05-15% of the weight of the catalyst; the specific surface area of the carrier is 50-1800 m²The pore volume is 0.2-1.2 ml/g.

The catalyst is prepared by loading a multi-metal active component and/or an auxiliary agent on an aminated carrier by at least one of an impregnation method and a precipitation method.

The catalyst needs to be activated before being used in the reaction.

The catalyst activation treatment is carried out in a hydrogen atmosphere, and the activation conditions are as follows: the temperature is 100-600 ℃, the time is 0.5-10 h, and the air speed of hydrogen is 20-3000 h^-1。

Optionally, the raw material cyclohexylimine may be diluted with a solvent, or no other solvent may be added.

Preferably, no additional solvent is required to be added to the starting cycloheximide.

The reaction raw material ammonia is selected from ammonia gas, liquid ammonia and ammonia water with the mass concentration of 5-28%.

Preferably, the feed ammonia is selected from liquid ammonia.

Optionally, the raw material, namely the cycloheximide and the ammonia, are mixed and then pumped into a preheater, and are preheated at 50-120 ℃ and then enter a reactor for reaction.

The cyclohexylimine amination reaction is carried out in a continuous or batch reactor.

Optionally, the continuous or batch reactor is selected from one of a fixed bed, a high pressure autoclave, a slurry bed, and a fluidized bed.

Preferably, the reactor is selected from fixed beds.

In the present application, the reaction is carried out under a hydrogen atmosphere, which means under the condition of introducing hydrogen.

The reaction conditions for ammoniation of the cycloheximide are as follows: the reaction temperature is 80-250 ℃, and preferably 120-200 ℃; the reaction pressure is 2-25 MPa, preferably 6-17 MPa; the molar ratio of the cycloheximide to the ammonia is 5: 1-1: 50, preferably 1: 1-1: 20; the volume space velocity of the cycloheximide is 0.02-20 h^-1Preferably 0.1 to 5 hours^-1(ii) a The volume space velocity of hydrogen gas is 2-1000 h^-1Preferably 10 to 300 hours^-1。

The invention is further illustrated by the following specific examples.

Example 1

Preparation and application of Ni5-Ru3-Os 1/activated carbon catalyst

9.1 g of 20-40 mesh active carbon is taken and treated for 1h at 150 ℃ in the atmosphere of ammonia gas. A20 ml portion containing 2.477 g of Ni (NO)₃)₂·6H₂O, 0.776 g RuCl₃·3H₂O, 0.184 g OsCl₃·3H₂And (3) soaking the active carbon carrier in an aqueous solution of O, naturally airing, drying at 120 ℃ for 4h, and roasting at 500 ℃ for 6h in an argon atmosphere. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 450 ℃ and 500h of hydrogen volume space velocity^-1And the time is 4 h. After the reduction process is finished, the temperature of the reactor is adjusted to 160 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and the ammonia are mixed according to the molar ratio of 1:10, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 40h^-1The hourly space velocity of the cycloheximide liquid is 0.9h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is gas chromatography, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (field induced fluorescence) detector and isobutanol as an internal standard, and the analytical results are shown in table 1.

Example 2

Ni5-Re2-W0.5/Al₂O₃Preparation and use of catalysts

Taking 9.25 g of 20-40 mesh Al₂O₃And treating for 2h at 200 ℃ in an ammonia atmosphere. A20 ml portion containing 2.477 g of Ni (NO)₃)₂·6H₂O, 0.288 g NH₄ReO₄0.077 g (NH)₄)₂WO₄With which the above-mentioned Al is impregnated₂O₃And (3) naturally airing the carrier, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 450 ℃ for 6 h. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 390 ℃ temperature and 500h of hydrogen volume space velocity^-1And the time is 5 h. The reduction process is finishedThen, the temperature of the reactor is adjusted to 150 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and ammonia are mixed according to the molar ratio of 1:5, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 50h^-1The hourly space velocity of the cycloheximide liquid is 0.6h^-1. The product stream comprises predominantly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is gas chromatography, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (field induced fluorescence) detector and isobutanol as an internal standard, and the analytical results are shown in table 1.

Example 3

Preparation and application of Fe8-Re 3-Ir1.5/activated carbon catalyst

8.75 g of 60-80 mesh active carbon is taken and treated for 2h at 150 ℃ in an ammonia atmosphere. Dispersing activated carbon in water to form a suspension, and stirring at a constant temperature of 50 ℃ at a medium speed. The formulation contained 3.465 g Fe (NO)₃)₃0.432 g NH₄ReO₄0.275 g of IrCl₃·3H₂O precursor fluid. The precipitant used was a 4mol/L KOH solution. Dripping precursor liquid and precipitant into the above suspension at the rate of 1ml/min, maintaining pH at 9 until precipitation is complete, washing the precipitate with deionized water to neutrality, filtering, air drying, oven drying at 120 deg.C for 4h, and calcining at 500 deg.C for 4h under argon atmosphere. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 400 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 4 h. After the reduction process is finished, the temperature of the reactor is adjusted to 170 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and the ammonia are mixed according to the molar ratio of 1:10, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 30h^-1The hourly space velocity of the cycloheximide liquid is 0.4h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. FixingAnd (3) sampling and analyzing after the bed reaction is carried out for 20 hours, wherein an analytical instrument is a gas chromatograph, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (flame ionization detector) and isobutanol as an internal standard, and the analytical results are shown in table 1.

Example 4

Ru5-Re1/SiO₂Preparation and use of catalysts

Taking 9.4 g of 20-40 mesh SiO₂And treating for 4h at 200 ℃ in an ammonia atmosphere. The preparation 20ml contains 1.293 g RuCl₃·3H₂O, 0.144 g NH₄ReO₄By impregnating the above SiO with the aqueous solution₂And naturally drying the carrier, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 400 ℃ for 3 h. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 300 ℃ and 1500h of hydrogen volume space velocity^-1And the time is 6 h. After the reduction process is finished, the temperature of the reactor is adjusted to 160 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and the ammonia are mixed according to the molar ratio of 1:15, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 25h^-1The hourly space velocity of the cycloheximide liquid is 0.4h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is gas chromatography, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (field induced fluorescence) detector and isobutanol as an internal standard, and the analytical results are shown in table 1.

Example 5

Re7-Co1.5/Al₂O₃Preparation and use of catalysts

Taking 9.15 g of 20-40 mesh Al₂O₃And treating for 6h at 300 ℃ in an ammonia atmosphere. The 20ml portion contained 1.008 g NH₄ReO₄0.741 g of Co (NO)₃)₂·6H₂An aqueous solution of O, and impregnating the Al with the aqueous solution₂O₃And naturally drying the carrier, drying the carrier at 120 ℃ for 4 hours, and roasting the carrier in a muffle furnace at 500 ℃ for 4 hours. The catalyst is subjected to reduction activation in a fixed bed device before reactionActivation treatment, wherein the activation conditions are as follows: 0.1MPa, 390 ℃ temperature and 1500h hydrogen volume space velocity^-1And the time is 4 h. After the reduction process is finished, the temperature of the reactor is adjusted to 150 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and the ammonia are mixed according to the molar ratio of 1:10, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of hydrogen is 30h^-1The hourly space velocity of the cycloheximide liquid is 0.5h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is a gas chromatograph, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (flame ionization detector) and isobutanol as an internal standard, and the analytical results are shown in table 1.

Example 6

Ru10-Re2-Cu1/Al₂O₃Preparation and use of catalysts

Taking 8.7 g of 20-40 mesh Al₂O₃And treating for 8h at 250 ℃ in an ammonia atmosphere. The 20ml solution containing 2.586 g of RuCl was prepared₃·3H₂O, 0.288 g NH₄ReO₄0.295 g of Cu (NO)₃)₂The Al is impregnated with the aqueous solution of (1)₂O₃And (3) naturally airing the carrier, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 400 ℃ for 6 h. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 300 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 6 h. After the reduction process is finished, the temperature of the reactor is adjusted to 160 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and ammonia are mixed according to the molar ratio of 1:20, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 20h^-1The hourly space velocity of the cycloheximide liquid is 0.3h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. Sampling and analyzing after the fixed bed reaction for 20h, wherein an analyzer is in gas phase colorThe spectrum is quantitatively analyzed by using an SE-30 capillary chromatographic column, an FID detector and isobutanol as an internal standard, and the analysis results are shown in Table 1.

Example 7

Ni6-Ru3-Re2/SiO₂Preparation and use of catalysts

Taking 8.9 g of 60-80 mesh SiO₂And treating for 6h at 250 ℃ in an ammonia atmosphere. Mixing SiO₂Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. The formulation contained 2.973 g of Ni (NO)₃)₂·6H₂O, 0.776 g RuCl₃·3H₂O, 0.288 g NH₄ReO₄The precursor liquid of (4). The precipitant used was a 4mol/L KOH solution. Dripping the precursor liquid and the precipitant into the suspension at the rate of 1ml/min, keeping the pH value at 9 until the precipitation is complete, washing the precipitate with deionized water to be neutral, filtering, airing, drying at 120 ℃ for 4h, and roasting at 450 ℃ in a muffle furnace for 8 h. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 400 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 6 h. After the reduction process is finished, the temperature of the reactor is adjusted to 170 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and ammonia are mixed according to the molar ratio of 1:25, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 70h^-1The hourly space velocity of the cycloheximide liquid is 0.6h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is gas chromatography, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (field induced fluorescence) detector and isobutanol as an internal standard, and the analytical results are shown in table 1. In order to evaluate the stability of the catalyst, samples were taken every 24 hours and analyzed, and the results of the sample analysis after 1000 hours of reaction showed that the catalyst activity and the 1, 6-hexanediamine selectivity remained substantially unchanged.

Example 8

Ni15-Re2.5-Mo0.5/Al₂O₃Preparation and use of catalysts

Taking 8.2 g of 20-40 mesh Al₂O₃And treating for 2h at 350 ℃ in an ammonia atmosphere. A20 ml portion containing 7.432 g of Ni (NO)₃)₂·6H₂O, 0.360 g NH₄ReO₄0.086 g (NH)₄)₂MoO₄With which the above-mentioned Al is impregnated₂O₃And (3) naturally airing the carrier, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 500 ℃ for 5 h. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 450 ℃ and 1500h of hydrogen volume space velocity^-1And the time is 4 h. After the reduction process is finished, the temperature of the reactor is adjusted to 150 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and the ammonia are mixed according to the molar ratio of 1:15, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 80h^-1The hourly space velocity of the cycloheximide liquid is 0.7h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is gas chromatography, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (field induced fluorescence) detector and isobutanol as an internal standard, and the analytical results are shown in table 1.

Example 9

Fe7-Ni7-Mo2/SiO₂Preparation and use of catalysts

Taking 8.4 g of 20-40 mesh SiO₂And treating for 3h at 250 ℃ in an ammonia atmosphere. A20 ml portion was prepared containing 3.032 g Fe (NO)₃)₃3.468 g Ni (NO)₃)₂·6H₂O, 0.408 g (NH)₄)₂MoO₄By impregnating the above SiO with the aqueous solution₂And (3) naturally airing the carrier, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 450 ℃ for 6 h. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 450 ℃ and 1200h of hydrogen volume space velocity^-1And the time is 8 h. After the reduction process is finished, the temperature of the reactor is adjusted to 160 ℃, the pressure is 8MPa, and the cyclohexylimine and ammonia are treated with ammonia after the system is stableMixing the raw materials according to the ratio of 1:15, preheating the mixture at 100 ℃, and pumping the preheated mixture into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 100h^-1The hourly space velocity of the cycloheximide liquid is 1.5h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is a gas chromatograph, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (flame ionization detector) and isobutanol as an internal standard, and the analytical results are shown in table 1.

Example 10

Fe11-Ru3-Rh1/Al₂O₃Preparation and application of catalyst

Taking 8.5 g of 20-40 mesh Al₂O₃And treating for 3h at 450 ℃ in an ammonia atmosphere. A20 ml portion containing 4.764 g Fe (NO)₃)₃0.776 g RuCl₃·3H₂O, 0.253 g RhCl₃·3H₂Aqueous solution of O, and impregnation of the above Al with the aqueous solution₂O₃And (3) naturally airing the carrier, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 350 ℃ for 6 h. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 400 ℃ and 600h of hydrogen volume space velocity^-1And the time is 10 h. After the reduction process is finished, the temperature of the reactor is adjusted to 160 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and the ammonia are mixed according to the molar ratio of 1:20, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 50h^-1The hourly space velocity of the cycloheximide liquid is 1h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is gas chromatography, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (field induced fluorescence) detector and isobutanol as an internal standard, and the analytical results are shown in table 1.

Comparative example 1

Evaluation of reaction of Raney Ni catalyst

The commercially available Raney Ni catalyst is filled in a fixed bed reactor, the temperature of the reactor is 160 ℃, the pressure is 8MPa, after a system is stable, the cycloheximide and ammonia are mixed according to the molar ratio of 1:10, and the mixture is preheated at 100 ℃ and then pumped into the fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 50h^-1The hourly space velocity of the cycloheximide liquid is 0.5h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is gas chromatography, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (field induced fluorescence) detector and isobutanol as an internal standard, and the analytical results are shown in table 1.

Comparative example 2

Co10/SiO₂Preparation and use of catalysts

Taking 9.0 g of 20-40 mesh SiO₂And the treatment in ammonia atmosphere is not performed. A20 ml aliquot of the mixture containing 4.939 grams of Co (NO)₃)₂·6H₂An aqueous solution of O, impregnating the above SiO with the aqueous solution₂And (3) naturally airing the carrier, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 400 ℃ for 4 h. Before reaction, the catalyst is subjected to reduction activation treatment in a fixed bed device, and the activation conditions are as follows: 0.1MPa, 350 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 5 h. After the reduction process is finished, the temperature of the reactor is adjusted to 160 ℃, the pressure is 8MPa, after the system is stable, the cycloheximide and the ammonia are mixed according to the molar ratio of 1:20, and the mixture is preheated at 100 ℃ and then pumped into a fixed bed reactor for catalytic reaction, wherein: the volume space velocity of the hydrogen is 60h^-1The hourly space velocity of the cycloheximide liquid is 0.5h^-1. The product stream comprises mainly the main product 1, 6-hexamethylenediamine, and the by-products are dimers comprising N- (6-aminohexyl) -1, 6-hexamethylenediamine, N- (6-aminohexyl) -hexamethyleneimine, and unreacted cyclohexylimine, ammonia and hydrogen. And (3) sampling and analyzing after the fixed bed reacts for 20 hours, wherein an analytical instrument is gas chromatography, quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID (field induced fluorescence) detector and isobutanol as an internal standard, and the analytical results are shown in table 1.

TABLE 1 data for the amination of cycloheximide to produce 1, 6-hexanediamine for the examples and comparative examples

From the above experimental results, it can be determined that one or more of the following can be achieved by using the catalyst for preparing 1, 6-hexamethylenediamine by aminating cyclohexylimine: (1) the preparation process of the catalyst is simple and easy to operate; (2)1, 6-hexamethylene diamine has high selectivity; (3) the generated by-product amine has few kinds and low selectivity; (4) the catalyst has high activity; (5) the economical efficiency of the process for synthesizing the 1, 6-hexanediamine is good; (6) the catalyst has good stability; (7) the reaction condition is mild; (8) continuous production can be realized; (9) the reaction process is green and clean.

Claims

1. The method for preparing 1, 6-hexamethylene diamine by aminating hexamethylene imine is characterized in that the adopted catalyst consists of three parts of active components, auxiliaries and carriers:

the active component is one or the combination of more than two of transition metals of Ni, Fe, Ru and Re;

the auxiliary agent is one of W, Ir, Os, Co, Cu, Rh and Mo;

the weight of the active component accounts for 5-45% of the weight of the catalyst;

the weight of the auxiliary agent accounts for 0.05-8% of the weight of the catalyst;

the carrier is selected from Al subjected to ammoniation treatment₂O₃Activated carbon, SiO_2、Al₂O₃-SiO₂One or a combination of two or more of (a);

the carrier ammonification treatment process is to contact the carrier and an ammonia source for 0.5 to 10 hours at the temperature of 100 to 500 ℃;

the ammonia source is selected from one or a combination of more than two of ammonia gas and liquid ammonia.

2. The method of claim 1, wherein:

the specific surface area of the carrier is 50-1800 m²The pore volume is 0.2-1.2 ml/g.

3. The method of claim 1, wherein the catalyst is prepared by at least one of impregnation or precipitation;

soaking the ammoniated carrier in a solution containing an active metal element source and an auxiliary agent element source, drying and roasting to obtain the catalyst;

or adding a solution containing an active metal element source and an auxiliary element source together with a precipitator into a suspension containing an ammoniated carrier, precipitating, aging, washing, drying and roasting to obtain the catalyst;

the roasting conditions are as follows: the temperature is 200-600 ℃, the time is 0.5-15 h, and when the used carrier is activated carbon in air and/or oxygen, the roasting atmosphere is one of nitrogen, argon and helium.

4. The method according to any one of claims 1 to 3, wherein in the presence of the catalyst, in a hydrogen atmosphere, cyclohexylimine and ammonia are converted into 1, 6-hexamethylenediamine, and the reaction raw material ammonia is selected from one or more of ammonia gas and liquid ammonia;

the reaction temperature is 80-250 ℃; the reaction pressure is 2-25 MPa; the molar ratio of the cycloheximide to the ammonia is 5: 1-1: 50; the volume space velocity of the cycloheximide is 0.02-20 h^-1(ii) a The volume space velocity of hydrogen gas is 2-1000 h^-1。

5. The method according to claim 4, wherein the catalyst is subjected to an activation treatment before the reaction, and the catalyst activation treatment is carried out in a hydrogen atmosphere under the following activation conditions: the temperature is 100-600 ℃, the pressure is 0.1MPa, the time is 0.5-10 h, and the air speed of hydrogen is 20-3000 h^-1。

6. According to claimThe method of claim 5, wherein the reaction temperature is 120 to 200 ℃; the reaction pressure is 6-17 MPa; the molar ratio of the cycloheximide to the ammonia is 1: 1-1: 20; the volume space velocity of the cycloheximide is 0.1-5 h^-1(ii) a The volume space velocity of hydrogen gas is 10-300 h^-1。