A method for preparing hexamethylenediamine

Abstract

The present invention relates to a method for preparing hexamethylenediamine. The method comprises the following steps: putting 6-hydroxycapronitrile, ammonia and a catalyst into a high-pressure reactor, then filling with hydrogen gas, and reacting at 100-200 °C with magnetic stirring for 10-24 h to obtain hexamethylenediamine; wherein, the molar ratio of 6-hydroxycapronitrile to ammonia is 1:5-20, the hydrogen gas pressure is 1-10 MPa, and the dosage of the catalyst is 1.0 wt% - 25.0 wt% of 6-hydroxycapronitrile. The catalyst composition includes a carrier and a loaded substance. The present invention prepares hexamethylenediamine by one-step catalytic amination reaction, avoiding the inherent safety hazards in the original process and solving the problem of shortage of the key raw material adiponitrile, and can realize the green and sustainable production of hexamethylenediamine.

Description

Technical Field

[0001] The present invention relates to a preparation technology of hexamethylenediamine, an important chemical raw material and intermediate, and particularly to a method for preparing hexamethylenediamine from 6-hydroxycapronitrile as an initial raw material and a catalyst therefor. Background Art

[0002] 1,6-Hexamethylenediamine (HMDA) is an extremely important chemical raw material and intermediate. Hexamethylenediamine is mainly used to react with adipic acid to produce polyhexamethylene adipamide (commonly known as nylon 66), and react with sebacic acid to produce polysebacoyl hexamethylenediamine products (commonly known as nylon 610). Nylon 66 is a thermoplastic resin and can be used to prepare engineering plastics, food packaging films, mechanical equipment parts, synthetic fibers, etc. Nylon 610 has high strength, good impact toughness, excellent wear resistance, oil resistance and self-lubrication, and is widely used in manufacturing gears, bearings, gaskets, sealing materials, oil storage containers and pipelines, textile machinery parts, etc. According to data, the global market size of nylon 66 in 2017 was 5.09 billion US dollars, and the compound annual growth rate from 2017 to 2026 is expected to be 3.1%, reaching 6.7 billion US dollars by 2026.

[0003] Currently, the production methods of hexamethylenediamine include adiponitrile (ADN) hydrogenation method, caprolactam (CPL) ammoniation method, adipaldehyde ammoniation method, hexanediol (HDO) ammoniation method, etc., but almost all large-scale industrial productions adopt the adiponitrile hydrogenation method. The traditional production process route of adiponitrile involves the use of toxic and dangerous raw materials, seriously threatening environmental safety, and its production technology is mainly mastered by four enterprises, namely Invista, Ascend, BASF, and Asahi Kasei. There is no domestic enterprise that can produce adiponitrile independently in China. It is mainly imported domestically, and the price is controlled by foreign suppliers. Coupled with the restrictions of import tariffs, international trade, force majeure and other factors, to a certain extent, it restricts the development of China's nylon 66 industry and HDI industry. The growing market demand for hexamethylenediamine and the high dependence on imported raw materials have led to a serious supply gap of hexamethylenediamine in China.

[0004] In the current technology, a new technical route has been developed to synthesize 6-hydroxycapronitrile by ammoniation starting from ε-caprolactone, and 6-hydroxycapronitrile is further ammoniated to produce adiponitrile (patent application number: CN202210371447.4). The most important use of adiponitrile is to further hydrogenate to produce hexamethylenediamine. However, it takes two steps to prepare hexamethylenediamine from 6-hydroxycapronitrile as the raw material, resulting in increased fixed asset investment and production costs. Therefore, it is of great value to develop a new process for directly preparing hexamethylenediamine by one-step catalytic ammoniation reaction from 6-hydroxycapronitrile. Summary of the Invention

[0005] The object of the present invention is to solve the deficiencies of the prior art and provide a method for preparing hexamethylenediamine. This method uses non-toxic, harmless, cheap and easily available 6-hydroxycapronitrile as the starting material and prepares hexamethylenediamine through a one-step catalytic amination reaction. The present invention avoids the inherent safety hazards existing in the original process and solves the problem of the shortage of the key raw material adiponitrile, and can realize the green and sustainable production of hexamethylenediamine.

[0006] The technical solution of the present invention is as follows:

[0007] A method for preparing hexamethylenediamine, the method comprising the following steps:

[0008] Put 6-hydroxycapronitrile, ammonia and a catalyst into a high-pressure reactor, then fill with hydrogen, and react at 100-200 °C with magnetic stirring for 10-24 h to obtain hexamethylenediamine;

[0009] Among them, the molar ratio of 6-hydroxycapronitrile: ammonia = 1:5-20, the hydrogen pressure is 1-10 MPa, and the catalyst dosage is 1.0 wt% - 25.0 wt% of 6-hydroxycapronitrile.

[0010] The ammonia is ammonia gas, liquid ammonia or ammonia water.

[0011] The composition of the catalyst includes a carrier and a load; among them, the load is the catalytic active component; the content of the catalytic active component is 1-30% of the total mass of the catalyst;

[0012] The catalytic active component of the catalyst is one or more of metal M;

[0013] The particle size range of the catalyst is: 20 mesh - 350 mesh;

[0014] The carrier is Al 2 O 3 、SiO 2 、TiO 2 、MgO、CeO 2 、ZrO 2 or a mixture thereof.

[0015] The metal M is one or more of Ni, Cu, Fe, Co, Ru, Pt.

[0016] The catalyst is obtained by calcining and reducing a catalyst precursor;

[0017] The preparation method of the precursor is the impregnation method, the deposition precipitation method or the ammonia evaporation method, and its composition includes a carrier and a load, and the load of the precursor is an oxide of metal M;

[0018] The calcination temperature of the catalyst precursor is 300-800 °C.

[0019] The reduction temperature of the catalyst precursor is 250-750 °C.

[0020] The catalyst carrier is preferably a mixture of Al 2 O 3 and MgO, and the metal M is preferably Co, Fe, Cu, Pt, Ru.

[0021] The beneficial effects of the present invention are as follows:

[0022] The present invention provides a new method for synthesizing hexamethylenediamine from 6-hydroxycapronitrile, which can solve the problems of difficult existing production processes, high risk coefficients, and shortage of raw materials. Moreover, the catalyst used in the invention is simple to prepare and can be prepared by conventional methods; the active components of the catalyst are metals such as Ni, Cu, Fe, Co, Pt, Ru, etc.

[0023] 6-Hydroxycapronitrile has the advantages of being non-toxic and harmless and having a simple preparation process. It is obtained by catalytic amination and cyanidation of ε-caprolactone, and ε-caprolactone comes from the deep processing industrial chain of by-products of coal coking pure benzene: coal → benzene → cyclohexane → cyclohexanone → ε-caprolactone, which provides a guarantee for the sufficient supply of ε-caprolactone, does not require petroleum, and conforms to the national strategic development idea;

[0024] The catalytic reaction of the present invention has economic feasibility. The by-products in the catalytic process are pollution-free and there is little three wastes. The conversion rate of 6-hydroxycapronitrile is as high as 100%, and the yield of hexamethylenediamine is 38.14%. In summary, the catalyst described in the invention is simple to prepare; the reaction raw materials are cheap, the production process is simple, there is little three wastes, and there is no pollution. Specific embodiments

[0025] The synthesis route of the present invention is as follows:

[0026]

[0027] The technical features of the present invention are further introduced below through examples:

[0028] Example 1: Preparation of catalyst I Co 10 / Al 2 O 3

[0029] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O and dissolve it in 40 mL of water, and add 0.9 g of γ-Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3Dissolve 3.84 g of NaOH in 50.0 mL of deionized water to obtain an alkaline solution; slowly add the alkaline solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 20 mesh - 50 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. Grind the calcined solid again and transfer it to a tubular furnace, and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h to obtain catalyst I Co with a cobalt loading of 10% 10 / Al 2 O 3 。

[0030] Example 2: Preparation of catalyst I Co by precipitation deposition method 1 / Al 2 O 3

[0031] Weigh 0.04938 g of Co(NO 3 ) 2 ·6H 2 O and dissolve it in 40 mL of water, add 0.9 g of γ-Al 2 O 3 and stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkaline solution; slowly add the alkaline solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 50 mesh - 100 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. Grind the calcined solid again and transfer it to a tubular furnace, and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h to obtain catalyst I Co with a cobalt loading of 1% 1 / Al 2 O 3 。

[0032] Example 3: Preparation of catalyst I Co by precipitation deposition method 30 / Al 2 O 3

[0033] Weigh 1.4814 g of Co(NO 3 ) 2 ·6H2 Dissolve it in 40 mL of water, and add 0.9 g of γ-Al 2 O 3 Stir it in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH are dissolved in 50.0 mL of deionized water to obtain an alkali solution; the alkali solution is slowly added dropwise to the reaction solution until the pH is about 10.0, and then the temperature is raised to 70 °C for aging for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry it for 12 h to obtain a catalyst precursor (particle size 100 mesh - 150 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine it at a heating rate of 5 °C / min to 500 °C for 3 h. After the calcined solid is ground again, transfer it to a tubular furnace and reduce it at a heating rate of 5 °C / min to 500 °C in a hydrogen atmosphere for 3 h to obtain catalyst I Co with a cobalt loading of 30% 30 / Al 2 O 3 。

[0034] Example 4: Preparation of catalyst I Ru by precipitation deposition method 5 / Al 2 O 3

[0035] Weigh 0.1026 g of RuCl 3 ·xH 2 O and dissolve it in 40 mL of water, and add 0.89 g of γ-Al 2 O 3 Stir it in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH are dissolved in 50.0 mL of deionized water to obtain an alkali solution; the alkali solution is slowly added dropwise to the reaction solution until the pH is about 10.0, and then the temperature is raised to 70 °C for aging for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry it for 12 h to obtain a catalyst precursor (particle size 150 mesh - 200 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine it at a heating rate of 5 °C / min to 500 °C for 3 h. After the calcined solid is ground again, transfer it to a tubular furnace and reduce it at a heating rate of 5 °C / min to 500 °C in a hydrogen atmosphere for 3 h to obtain catalyst I Ru with a ruthenium loading of 5% 5 / Al 2 O 3 。

[0036] Example 5: Preparation of catalyst I Co 10 Cu5 / Al 2 O 3

[0037] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.1887 g of Cu(NO 3 ) 2 ·3H 2 O and dissolve them in 40 mL of water. Add 0.85 g of γ-Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkali solution. Slowly add the alkali solution to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 5 °C / min to 500 °C for 3 h. After calcining, grind the solid again and transfer it to a tubular furnace. Under a hydrogen atmosphere, raise the temperature to 500 °C at 5 °C / min and reduce for 3 h. Obtain catalyst I Co 10 Cu 5 / Al 2 O 3 .

[0038] Example 6: Preparation of catalyst I Co 10 Fe 5 / Al 2 O 3

[0039] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.3607 g of Fe(NO 3 ) 2 ·9H 2 O and dissolve them in 40 mL of water. Add 0.85 g of γ-Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3Dissolve 3.84 g of NaOH in 50.0 mL of deionized water to obtain an alkali solution; slowly add the alkali solution to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. Grind the calcined solid again and transfer it to a tubular furnace, and reduce it at 700 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h. Obtain catalyst I Co with a cobalt loading of 10% and an iron loading of 5% 10 Fe 5 / Al 2 O 3 。

[0040] Example 7: Preparation of catalyst I Co by precipitation deposition method 10 Pt 1 / Al 2 O 3

[0041] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.01635 g of Pt(NO 3 ) 2 Dissolve in 40 mL of water, add 0.89 g of γ-Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkali solution; slowly add the alkali solution to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. Grind the calcined solid again and transfer it to a tubular furnace, and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h. Obtain catalyst ICo with a cobalt loading of 10% and a platinum loading of 1% 10 Pt 1 / Al 2 O 3 。

[0042] Example 8: Preparation of catalyst I Co by precipitation deposition method 10Ru 1 / Al 2 O 3

[0043] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.89 g of γ-Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkali solution; slowly add the alkali solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 5 °C / min to 500 °C for 3 h. After the calcined solid is ground again, transfer it to a tubular furnace and reduce it to 500 °C at 5 °C / min in a hydrogen atmosphere for 3 h. Obtain a catalyst ICo 10 Ru 1 / Al 2 O 3 。

[0044] Example 9: Preparation of catalyst I Co 10 Ru 1 / TiO 2

[0045] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.89 g of TiO 2 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3Dissolve 3.84 g of NaOH in 50.0 mL of deionized water to obtain an alkali solution; slowly add the alkali solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. After re-grinding the calcined solid, transfer it to a tubular furnace and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h.

[0046] Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / TiO 2 。

[0047] Example 10: Preparation of catalyst I Co 10 Ru 1 / MgO

[0048] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water, add 0.89 g of MgO and stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkali solution; slowly add the alkali solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. After re-grinding the calcined solid, transfer it to a tubular furnace and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h.

[0049] Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / MgO.

[0050] Example 11: Preparation of catalyst I Co 10 Ru 1 / SiO 2

[0051] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.89 g of SiO 2 and stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkali solution. Slowly add the alkali solution to the reaction solution until the pH is about 10.0, and then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at a heating rate of 5 °C / min to 500 °C for 3 h. After re-grinding the calcined solid, transfer it to a tubular furnace and reduce it in a hydrogen atmosphere at a heating rate of 5 °C / min to 500 °C for 3 h.

[0052] Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / SiO 2 .

[0053] Example 12: Preparation of catalyst I Co 10 Ru 1 / ZrO 2

[0054] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.89 g of ZrO 2 and stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3Dissolve 3.84 g of NaOH in 50.0 mL of deionized water to obtain an alkali solution; slowly add the alkali solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. After re-grinding the calcined solid, transfer it to a tubular furnace and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h.

[0055] Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / ZrO 2 。

[0056] Example 13: Preparation of catalyst I Co by precipitation deposition method 10 Ru 1 / CeO 2

[0057] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water, add 0.89 g of CeO 2 and stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkali solution; slowly add the alkali solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. After re-grinding the calcined solid, transfer it to a tubular furnace and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h.

[0058] Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / CeO 2 。

[0059] Example 14: Preparation of catalyst I Co by precipitation deposition method10 Ru 1 / CeO 2 -Al 2 O 3

[0060] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of CeO 2 and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkaline solution. Slowly add the alkaline solution to the reaction solution until the pH is about 10.0, and then raise the temperature to 70 °C for aging for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry it for 12 h to obtain a catalyst precursor (particle size: 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine it at a heating rate of 5 °C / min to 500 °C for 3 h. After re-grinding the calcined solid, transfer it to a tubular furnace and reduce it at a heating rate of 5 °C / min to 500 °C in a hydrogen atmosphere for 3 h. Obtain catalyst I Co 10 Ru 1 / CeO 2 -Al 2 O 3 .

[0061] Example 15: Preparation of catalyst I Co 10 Ru 1 / ZrO 2 -Al 2 O 3

[0062] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of ZrO 2 and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO3 Dissolve 3.84 g of NaOH in 50.0 mL of deionized water to obtain an alkaline solution; slowly add the alkaline solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. Grind the calcined solid again and transfer it to a tubular furnace, and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h. Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / ZrO 2 -Al 2 O 3 。

[0063] Example 16: Preparation of catalyst I Co 10 Ru 1 / TiO 2 -Al 2 O 3

[0064] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water, add 0.445 g of TiO 2 and 0.445 g of Al 2 O 3 and stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkaline solution; slowly add the alkaline solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. Grind the calcined solid again and transfer it to a tubular furnace, and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h. Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / TiO 2-Al 2 O 3 。

[0065] Example 17: Preparation of Catalyst I Co 10 Ru 1 / SiO 2 -Al 2 O 3

[0066] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of SiO 2 and 0.445 g of Al 2 O 3 and stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkali solution. Slowly add the alkali solution dropwise to the reaction solution until the pH is about 10.0, and then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine it at a heating rate of 5 °C / min to 500 °C for 3 h. After re-grinding the calcined solid, transfer it to a tubular furnace and reduce it in a hydrogen atmosphere at a heating rate of 5 °C / min to 500 °C for 3 h. Obtain Catalyst I Co 10 Ru 1 / SiO 2 -Al 2 O 3 。

[0067] Example 18: Preparation of Catalyst I Co 10 Ru 1 / MgO-Al 2 O 3

[0068] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of MgO and 0.445 g of Al2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH are dissolved in 50.0 mL of deionized water to obtain an alkali solution; the alkali solution is slowly added dropwise to the reaction solution until the pH is about 10.0, and then the temperature is raised to 70 °C for aging for 2 h. After cooling to room temperature, the precipitate is collected by centrifugation, and the precipitate is washed with deionized water until the pH of the supernatant is neutral. The obtained precipitate is placed in an oven at 100 °C and dried for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After the catalyst precursor is sufficiently ground, it is placed in a muffle furnace and calcined at 5 °C / min to 500 °C for 3 h. The calcined solid is ground again and transferred to a tubular furnace, and reduced at 5 °C / min to 500 °C for 3 h in a hydrogen atmosphere. Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / MgO - Al 2 O 3 .

[0069] Example 19: Preparation of catalyst I Co 10 Ru 1 / MgO - Al 2 O 3

[0070] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve in 40 mL of water, add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. After dispersing evenly, add concentrated ammonia water to adjust the pH to 11 - 12, continue stirring for 4 h, then raise the temperature to 80 °C for ammonia evaporation, and stop ammonia evaporation when the pH reaches about 7.00. Centrifuge to collect the precipitate, and wash the precipitate with deionized water 3 times. The precipitate is dried in an oven at 80 °C for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After the catalyst precursor is sufficiently ground, it is placed in a muffle furnace and calcined at 5 °C / min to 500 °C for 3 h. The calcined solid is ground again and transferred to a tubular furnace, and reduced at 5 °C / min to 500 °C for 3 h in a hydrogen atmosphere. Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / MgO - Al 2 O 3 .

[0071] Example 20: Preparation of Catalyst I Co 10 Ru 1 / MgO-Al 2 O 3

[0072] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 2 mL of water. Add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir evenly. After ultrasonic treatment for 4 h, impregnate at room temperature for 24 h to obtain the catalyst precursor. The catalyst precursor is dried in an oven at 80 °C for 12 h to obtain the catalyst precursor (particle size is 150 mesh - 350 mesh). The catalyst precursor is thoroughly ground and then placed in a muffle furnace, calcined at a heating rate of 5 °C / min to 500 °C for 3 h. The calcined solid is ground again and transferred to a tubular furnace, and reduced in a hydrogen atmosphere at a heating rate of 5 °C / min to 500 °C for 3 h. Obtain Catalyst I Co 10 Ru 1 / MgO-Al 2 O 3 .

[0073] Example 21: Preparation of Catalyst I Co 1 Ru 1 / MgO-Al 2 O 3

[0074] Weigh 0.0988 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3Dissolve 3.84 g of NaOH in 50.0 mL of deionized water to obtain an alkaline solution; slowly add the alkaline solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. Grind the calcined solid again and transfer it to a tube furnace, and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h. Obtain catalyst I Co with a cobalt loading of 1% and a ruthenium loading of 1% 1 Ru 1 / MgO-Al 2 O 3 。

[0075] Example 22: Preparation of catalyst I Co by precipitation deposition method 25 Ru 1 / MgO-Al 2 O 3

[0076] Weigh 1.4815 g of Co(NO 3 ) 2 ·6H 2 O, 0.0246 g of RuCl 3 ·xH 2 O and dissolve in 40 mL of water, add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH are dissolved in 50.0 mL of deionized water to obtain an alkaline solution; slowly add the alkaline solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at 500 °C at a heating rate of 5 °C / min for 3 h. Grind the calcined solid again and transfer it to a tube furnace, and reduce it at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h. Obtain catalyst I Co with a cobalt loading of 25% and a ruthenium loading of 1% 25 Ru 1 / MgO-Al 2 O 3 。

[0077] Example 23: Preparation of Catalyst I Co by Precipitation Deposition Method 25 Ru 0.1 / MgO-Al 2 O 3

[0078] Weigh 1.4723 g of Co(NO 3 ) 2 ·6H 2 O, 0.00245 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkali solution. Slowly add the alkali solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at a heating rate of 5 °C / min to 500 °C for 3 h. After calcining, grind the solid again and transfer it to a tubular furnace. Reduce it in a hydrogen atmosphere at a heating rate of 5 °C / min to 500 °C for 3 h. Obtain a catalyst I Co 25 Ru 0.1 / MgO-Al 2 O 3 .

[0079] Example 24: Preparation of Catalyst I Co by Precipitation Deposition Method 25 Ru 10 / MgO-Al 2 O 3

[0080] Weigh 1.6905 g of Co(NO 3 ) 2 ·6H 2 O, 0.2809 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 33.84 g of NaOH was dissolved in 50.0 mL of deionized water to obtain an alkaline solution; the alkaline solution was slowly added dropwise to the reaction solution until the pH was about 10.0, and then the temperature was raised to 70 °C for aging for 2 h. After cooling to room temperature, the precipitate was collected by centrifugation, and the precipitate was washed with deionized water until the pH of the supernatant was neutral. The obtained precipitate was placed in an oven at 100 °C and dried for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). The catalyst precursor was fully ground and then placed in a muffle furnace, calcined at 500 °C at a heating rate of 5 °C / min for 3 h. The calcined solid was ground again and transferred to a tubular furnace, and reduced at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h. A catalyst I Co with a cobalt loading of 25% and a ruthenium loading of 10% was obtained 25 Ru 10 / MgO-Al 2 O 3 。

[0081] Example 25: Preparation of catalyst I Co by precipitation deposition method 10 Ru 5 / MgO-Al 2 O 3

[0082] Weighed 0.8050 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O was dissolved in 40 mL of water, 0.445 g of MgO and 0.445 g of Al 2 O 3 were added and stirred in a water bath at 60 °C. Took 5.09 g of Na 2 CO 3 and 3.84 g of NaOH were dissolved in 50.0 mL of deionized water to obtain an alkaline solution; the alkaline solution was slowly added dropwise to the reaction solution until the pH was about 10.0, and then the temperature was raised to 70 °C for aging for 2 h. After cooling to room temperature, the precipitate was collected by centrifugation, and the precipitate was washed with deionized water until the pH of the supernatant was neutral. The obtained precipitate was placed in an oven at 100 °C and dried for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). The catalyst precursor was fully ground and then placed in a muffle furnace, calcined at 500 °C at a heating rate of 5 °C / min for 3 h. The calcined solid was ground again and transferred to a tubular furnace, and reduced at 500 °C at a heating rate of 5 °C / min in a hydrogen atmosphere for 3 h. A catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 5% was obtained 10 Ru 5 / MgO-Al 2 O 3 。

[0083] Example 26: Preparation of Catalyst I Co by Precipitation Deposition Method 10 Ru 1 / MgO - Al 2 O 3

[0084] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkali solution. Slowly add the alkali solution to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at a heating rate of 5 °C / min to 300 °C for 3 h. After re - grinding the calcined solid, transfer it to a tubular furnace and reduce it in a hydrogen atmosphere at a heating rate of 5 °C / min to 500 °C for 3 h. Obtain Catalyst I Co 10 Ru 1 / MgO - Al 2 O 3 .

[0085] Example 27: Preparation of Catalyst I Co by Precipitation Deposition Method 10 Ru 1 / MgO - Al 2 O 3

[0086] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3Dissolve 3.84 g of NaOH in 50.0 mL of deionized water to obtain an alkaline solution; slowly add the alkaline solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at a heating rate of 5 °C / min to 800 °C for 3 h. After re-grinding the calcined solid, transfer it to a tubular furnace and reduce it in a hydrogen atmosphere at a heating rate of 5 °C / min to 500 °C for 3 h. Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / MgO-Al 2 O 3 。

[0087] Example 28: Preparation of catalyst I Co 10 Ru 1 / MgO-Al 2 O 3

[0088] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve in 40 mL of water, add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve in 50.0 mL of deionized water to obtain an alkaline solution; slowly add the alkaline solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate, and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at a heating rate of 5 °C / min to 500 °C for 3 h. After re-grinding the calcined solid, transfer it to a tubular furnace and reduce it in a hydrogen atmosphere at a heating rate of 5 °C / min to 250 °C for 3 h. Obtain catalyst I Co with a cobalt loading of 10% and a ruthenium loading of 1% 10 Ru 1 / MgO-Al 2 O 3 。

[0089] Example 29: Preparation of Catalyst I Co by Precipitation Deposition Method 10 Ru 1 / MgO - Al 2 O 3

[0090] Weigh 0.4938 g of Co(NO 3 ) 2 ·6H 2 O, 0.0205 g of RuCl 3 ·xH 2 O and dissolve them in 40 mL of water. Add 0.445 g of MgO and 0.445 g of Al 2 O 3 Stir in a water bath at 60 °C. Take 5.09 g of Na 2 CO 3 and 3.84 g of NaOH and dissolve them in 50.0 mL of deionized water to obtain an alkaline solution. Slowly add the alkaline solution dropwise to the reaction solution until the pH is about 10.0, then raise the temperature to 70 °C and age for 2 h. After cooling to room temperature, centrifuge to collect the precipitate and wash the precipitate with deionized water until the pH of the supernatant is neutral. Place the obtained precipitate in an oven at 100 °C and dry for 12 h to obtain a catalyst precursor (particle size 150 mesh - 350 mesh). After thoroughly grinding the catalyst precursor, place it in a muffle furnace and calcine at a heating rate of 5 °C / min to 500 °C for 3 h. After the calcined solid is ground again, transfer it to a tubular furnace and reduce it in a hydrogen atmosphere at a heating rate of 5 °C / min to 750 °C for 3 h. Obtain catalyst I Co 10 Ru 1 / MgO - Al 2 O 3 .

[0091] Example 30: Weigh 0.5 g of 6 - hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 1 into a 25 mL high - pressure reactor. At this time, the molar ratio of 6 - hydroxyhexanenitrile: ammonia = 1:15. Then add a high - temperature resistant magnetic stirring bar and then seal the high - pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously five times, then fill with 6 MPa of hydrogen and check the airtightness of the device. Place the gas - filled reaction kettle on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C and react for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6 - hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 7.57%.

[0092] Example 31: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 2 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxycapronitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. By gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 5.35%.

[0093] Example 32: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 3 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxycapronitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. By gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 6.58%.

[0094] Example 33: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 4 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxycapronitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. By gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 15.36%.

[0095] Example 34: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 5 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxycapronitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. By gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 10.72%.

[0096] Example 35: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 6 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 11.09%.

[0097] Example 36: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 7 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 14.65%.

[0098] Example 37: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 8 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 30.41%.

[0099] Example 38: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 9 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the reactor filled with gas on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 28.21%.

[0100] Example 39: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 10 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the reactor filled with gas on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 10.19%.

[0101] Example 40: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 11 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the reactor filled with gas on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 13.25%.

[0102] Example 41: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 12 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxycapronitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on a heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 7.87%.

[0103] Example 42: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 13 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxycapronitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on a heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 23.42%.

[0104] Example 43: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 14 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxycapronitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on a heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 27.84%.

[0105] Example 44: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 15 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 24.13%.

[0106] Example 45: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 16 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 30.82%.

[0107] Example 46: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 17 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 24.58%.

[0108] Example 47: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, continuously replace it five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 36.06%.

[0109] Example 48: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 19 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, continuously replace it five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 26.93%.

[0110] Example 49: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 20 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, continuously replace it five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 24.09%.

[0111] Example 50: Weigh 0.5 g of 6-hydroxyhexanenitrile, 25 mL of ammonia water (5 wt%) and 100 mg of the catalyst prepared in Example 21 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, continuously replace it five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reaction kettle on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 19.67%.

[0112] Example 51: Weigh 0.5 g of 6-hydroxyhexanenitrile, 12.5 mL of ammonia water (10 wt%) and 100 mg of the catalyst prepared in Example 22 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, continuously replace it five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reaction kettle on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 33.49%.

[0113] Example 52: Weigh 0.5 g of 6-hydroxyhexanenitrile, 8.3 mL of ammonia water (15 wt%) and 100 mg of the catalyst prepared in Example 23 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, continuously replace it five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reaction kettle on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 27.49%.

[0114] Example 53: Weigh 0.5 g of 6-hydroxycapronitrile, 6.25 mL of ammonia water (20 wt%) and 100 mg of the catalyst prepared in Example 24 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxycapronitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 30.91%.

[0115] Example 54: Weigh 0.5 g of 6-hydroxycapronitrile, 4.5 mL of ammonia water (28 wt%) and 100 mg of the catalyst prepared in Example 25 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxycapronitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 30.33%.

[0116] Example 55: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 26 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxycapronitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 25.32%.

[0117] Example 56: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 27 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 29.25%.

[0118] Example 57: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 28 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 26.42%.

[0119] Example 58: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 29 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, then fill in 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 28.98%.

[0120] Example 59: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 36.06%.

[0121] Example 60: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 100 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 9.63%.

[0122] Example 61: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirrer, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 140 °C for 14 h. Through gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 12.52%.

[0123] Example 62: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxycapronitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 160 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 15.64%.

[0124] Example 63: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxycapronitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 200 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 28.02%.

[0125] Example 64: Weigh 0.5 g of 6-hydroxycapronitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxycapronitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 1 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxycapronitrile is 100%, and the yield of hexamethylenediamine is 16.58%.

[0126] Example 65: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 3 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 22.95%.

[0127] Example 66: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 7 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 27.06%.

[0128] Example 67: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 10 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 25.14%.

[0129] Example 68: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 5 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 10.35%.

[0130] Example 69: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 50 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 19.59%.

[0131] Example 70: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 150 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a heat-resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, replace it continuously for five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 14 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 29.69%.

[0132] Example 71: Weigh 0.5 g of 6-hydroxyhexanenitrile, 1.67 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL autoclave. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:5. Then add a heat-resistant magnetic stirring bar, and then seal the autoclave. Replace the air in the autoclave with hydrogen, replace it continuously for five times, then fill with 6 MPa of hydrogen and check the airtightness of the device. Place the autoclave filled with gas on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. By gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 14.68%.

[0133] Example 72: Weigh 0.5 g of 6-hydroxyhexanenitrile and 100 mg of the catalyst prepared in Example 18 into a 25 mL autoclave, then add a heat-resistant magnetic stirring bar, and then seal the autoclave. Replace the air in the autoclave with ammonia gas, replace it continuously for five times, then add 0.76 g of ammonia gas. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:10. Add 3 ml of deionized water with a high-pressure pump, then fill with 6 MPa of hydrogen and check the airtightness of the device. Place the autoclave filled with gas on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. By gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 22.04%.

[0134] Example 73: Weigh 0.5 g of 6-hydroxyhexanenitrile and 100 mg of the catalyst prepared in Example 18 into a 25 mL autoclave, then add a heat-resistant magnetic stirring bar, and then seal the autoclave. Replace the air in the autoclave with hydrogen, replace it continuously for five times. After replacement, add 1.53 g of liquid ammonia with a liquid ammonia pump. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:20. Finally, fill with 6 MPa of hydrogen and check the airtightness of the device. Place the autoclave filled with gas on the heating control device, set the rotation speed to 600 r / min, and heat to 190 °C for 14 h. By gas chromatography internal standard method detection and analysis, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 29.73%.

[0135] Example 74: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, continuously replace it five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 10 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 30.75%.

[0136] Example 75: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, continuously replace it five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 10 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 32.95%.

[0137] Example 76: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio of 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen, continuously replace it five times, and then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 16 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 38.14%.

[0138] Example 77: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen for five consecutive times, then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 18 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 33.29%.

[0139] Example 78: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen for five consecutive times, then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 20 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 29.42%.

[0140] Example 79: Weigh 0.5 g of 6-hydroxyhexanenitrile, 5 mL of ammonia water (25 wt%) and 100 mg of the catalyst prepared in Example 18 into a 25 mL high-pressure reactor. At this time, the molar ratio is 6-hydroxyhexanenitrile: ammonia = 1:15. Then add a high-temperature resistant magnetic stirring bar, and then seal the high-pressure reactor. Replace the air in the reactor with hydrogen for five consecutive times, then fill it with 6 MPa of hydrogen and check the airtightness of the device. Place the gas-filled reactor on the heating control device, set the rotation speed to 600 r / min, and heat it to 190 °C for 24 h. After detection and analysis by gas chromatography internal standard method, the conversion rate of 6-hydroxyhexanenitrile is 100%, and the yield of hexamethylenediamine is 26.57%.

[0141] Matters not covered by the present invention are well-known technologies.

Claims

1. A method for preparing hexamethylenediamine, characterized in that the method comprises the following steps: Put 6-hydroxycapronitrile, ammonia and a catalyst into a high-pressure reactor, then fill with hydrogen, and react at 160-200 °C with magnetic stirring for 10-24 h to obtain hexamethylenediamine; Wherein, The molar ratio is 6-hydroxycapronitrile: ammonia = 1:5-20, the hydrogen pressure is 3-10 MPa, and the catalyst dosage is 1.0 wt% - 25.0 wt% of 6-hydroxycapronitrile; The composition of the catalyst includes a carrier and a loaded substance; wherein the loaded substance is the catalytically active component; the content of the catalytically active component is 1-30% of the total mass of the catalyst; The catalytically active component of the catalyst is metal M; The ammonia is added in the form of ammonia water; The catalyst support described is a mixture of Al 2 O 3 and MgO, and the metal M is a mixture of Co and Ru.

2. The method for preparing hexamethylenediamine according to claim 1, Characterized in that The catalyst is obtained by calcining and reducing a catalyst precursor; The preparation method of the precursor is the impregnation method, the deposition-precipitation method or the ammonia evaporation method, and its composition includes a carrier and a loaded substance, and the loaded substance of the precursor is an oxide of metal M; The calcination temperature of the catalyst precursor is 300-800 °C; The reduction temperature of the catalyst precursor is 250-750 °C.

3. The method for preparing hexamethylenediamine according to claim 1, Characterized in that The particle size range of the catalyst is 20 mesh - 350 mesh.