Catalyst for synthesizing 1,3-cyclohexanedimethylamine by hydrogenation of m-xylylenediamine and preparation method thereof

Abstract

The invention relates to the technical field of catalysts, in particular to a catalyst for synthesizing 1,3-cyclohexanedimethylamine by hydrogenation of m-xylylenediamine and a preparation method thereof. The catalyst for the synthesis of 1,3-cyclohexanedimethylamine by the hydrogenation of m-xylylenediamine includes a carrier, an active component and a promoter doped on the carrier, and the catalyst carrier is SAPO-11 mesoporous molecular sieve, and the activity The component is metallic Ru, and the accelerator is one or more of Pr, Nd, Mo, Lu, and Tm. The catalyst for synthesizing 1,3-cyclohexanedimethylamine by hydrogenation of m-xylylenediamine of the present invention has the advantages of not easy loss of active components, long service life and high selectivity; the present invention also provides a preparation method thereof.

Description

technical field

[0001] The invention relates to the technical field of catalysts, in particular to a catalyst for synthesizing 1,3-cyclohexanedimethylamine by hydrogenation of m-xylylenediamine and a preparation method thereof. Background technique

[0002] 1,3-cyclohexanedimethylamine is an important chemical intermediate, which is widely used in the chemical industry. It is mainly used as a curing agent for epoxy resins. It has low volatility, is not easy to crystallize, fast curing speed, yellowing resistance, With the advantages of good weather resistance and good transparency, it is widely used in the fields of beauty joints, composite materials, epoxy floors and structural adhesives. Especially as a curing agent for beauty joints, it has an irreplaceable role. It can also be used to synthesize polyurethane with high refractive index and good transparency.

[0003] The hydrogenation method of m-xylylenediamine (MXDA) is the main production method of 1,3-cyclohexyldime...

Examples

Embodiment 1

[0048] (1) Preparation of SAPO-11 mesoporous molecular sieve with isomorphic replacement of Ru-Pr: The molar ratio of KH-560, pseudoboehmite, phosphoric acid, diisopropylamine and deionized water is 1:1.7:2:1.1: A scale of 40 weighs well. Add 11.7g pseudo-boehmite to a mixture of 23.1g phosphoric acid (concentration 85wt%), 11.1g diisopropylamine and 72.0g deionized water, add 1.9g hydrated ruthenium trichloride (ruthenium content 43wt%), 0.7 g Pr(NO 3 ) 3 , after stirring evenly, add 23.6g KH-560 respectively, stir fully at 25°C until a uniform gel is obtained, put the gel into a stainless steel autoclave and seal it, crystallize at a constant temperature of 120°C for 6 hours, and wait until the crystallization is complete, the product Centrifuge, wash with 80°C distilled water until the pH value remains constant, dry at 100°C, and calcinate in a muffle furnace at 400°C for 2 hours to obtain Ru-Pr isomorphously substituted SAPO-11.

[0049] (2) Organic amine modification: ...

Embodiment 2

[0052] (1) Preparation of SAPO-11 mesoporous molecular sieve with isomorphic substitution of Ru-Nd: The molar ratio of KH-560, pseudoboehmite, phosphoric acid, di-n-propylamine and deionized water is 1:1.8:1.9:1.2: A scale of 45 weighs well. Add 12.4g pseudoboehmite to a mixture of 21.9g phosphoric acid (concentration 85wt%), 12.1g di-n-propylamine and 81.0g deionized water, add 1.9g hydrated ruthenium trichloride (ruthenium content 43wt%), 0.5 g NdCl 3 , after stirring evenly, add 23.6g KH-560 respectively, stir fully at 25°C until a uniform gel is obtained, put the gel into a stainless steel autoclave and seal it, crystallize at a constant temperature of 130°C for 7 hours, and wait until the crystallization is complete, the product Centrifuge, wash with distilled water at 80°C until the pH value remains constant, dry at 100°C, and calcinate at 500°C in a muffle furnace for 1.5h to obtain Ru-Nd isomorphously substituted SAPO-11.

[0053] (2) Organic amine modification: The ...

Embodiment 3

[0056] (1) Preparation of SAPO-11 mesoporous molecular sieve with isomorphic replacement of Ru-Pr: The molar ratio of KH-590, pseudoboehmite, phosphoric acid, diisopropylamine and deionized water is 1:1.9:1.8:1.3: A scale of 50 weighs well. Add 15.4g pseudoboehmite to a mixture of 20.8g phosphoric acid (concentration 85wt%), 9.6g diethylamine and 90.0g deionized water, add 1.9g hydrated ruthenium trichloride (ruthenium content 43wt%), 0.5 g PrCl 3 , after stirring evenly, add 19.6g KH-590 respectively, stir fully at 25°C until a uniform gel is obtained, put the gel into a stainless steel autoclave and seal it, and crystallize at a constant temperature of 125°C for 8 hours. After the crystallization is complete, the product Centrifuge, wash with 80°C distilled water until the pH value remains unchanged, dry at 100°C, and calcinate in a muffle furnace at 450°C for 4 hours to obtain Ru-Pr isomorphously substituted SAPO-11.

[0057] (2) Organic amine modification: The molar rati...

technical field

[0001] The invention relates to the technical field of catalysts, in particular to a catalyst for synthesizing 1,3-cyclohexanedimethylamine by hydrogenation of m-xylylenediamine and a preparation method thereof. Background technique

[0002] 1,3-cyclohexanedimethylamine is an important chemical intermediate, which is widely used in the chemical industry. It is mainly used as a curing agent for epoxy resins. It has low volatility, is not easy to crystallize, fast curing speed, yellowing resistance, With the advantages of good weather resistance and good transparency, it is widely used in the fields of beauty joints, composite materials, epoxy floors and structural adhesives. Especially as a curing agent for beauty joints, it has an irreplaceable role. It can also be used to synthesize polyurethane with high refractive index and good transparency.

[0003] The hydrogenation method of m-xylylenediamine (MXDA) is the main production method of 1,3-cyclohexyldime...

Examples

Embodiment 1

[0048] (1) Preparation of SAPO-11 mesoporous molecular sieve with isomorphic replacement of Ru-Pr: The molar ratio of KH-560, pseudoboehmite, phosphoric acid, diisopropylamine and deionized water is 1:1.7:2:1.1: A scale of 40 weighs well. Add 11.7g pseudo-boehmite to a mixture of 23.1g phosphoric acid (concentration 85wt%), 11.1g diisopropylamine and 72.0g deionized water, add 1.9g hydrated ruthenium trichloride (ruthenium content 43wt%), 0.7 g Pr(NO 3 ) 3 , after stirring evenly, add 23.6g KH-560 respectively, stir fully at 25°C until a uniform gel is obtained, put the gel into a stainless steel autoclave and seal it, crystallize at a constant temperature of 120°C for 6 hours, and wait until the crystallization is complete, the product Centrifuge, wash with 80°C distilled water until the pH value remains constant, dry at 100°C, and calcinate in a muffle furnace at 400°C for 2 hours to obtain Ru-Pr isomorphously substituted SAPO-11.

[0049] (2) Organic amine modification: ...

Embodiment 2

[0052] (1) Preparation of SAPO-11 mesoporous molecular sieve with isomorphic substitution of Ru-Nd: The molar ratio of KH-560, pseudoboehmite, phosphoric acid, di-n-propylamine and deionized water is 1:1.8:1.9:1.2: A scale of 45 weighs well. Add 12.4g pseudoboehmite to a mixture of 21.9g phosphoric acid (concentration 85wt%), 12.1g di-n-propylamine and 81.0g deionized water, add 1.9g hydrated ruthenium trichloride (ruthenium content 43wt%), 0.5 g NdCl 3 , after stirring evenly, add 23.6g KH-560 respectively, stir fully at 25°C until a uniform gel is obtained, put the gel into a stainless steel autoclave and seal it, crystallize at a constant temperature of 130°C for 7 hours, and wait until the crystallization is complete, the product Centrifuge, wash with distilled water at 80°C until the pH value remains constant, dry at 100°C, and calcinate at 500°C in a muffle furnace for 1.5h to obtain Ru-Nd isomorphously substituted SAPO-11.

[0053] (2) Organic amine modification: The ...

Embodiment 3

[0056] (1) Preparation of SAPO-11 mesoporous molecular sieve with isomorphic replacement of Ru-Pr: The molar ratio of KH-590, pseudoboehmite, phosphoric acid, diisopropylamine and deionized water is 1:1.9:1.8:1.3: A scale of 50 weighs well. Add 15.4g pseudoboehmite to a mixture of 20.8g phosphoric acid (concentration 85wt%), 9.6g diethylamine and 90.0g deionized water, add 1.9g hydrated ruthenium trichloride (ruthenium content 43wt%), 0.5 g PrCl 3 , after stirring evenly, add 19.6g KH-590 respectively, stir fully at 25°C until a uniform gel is obtained, put the gel into a stainless steel autoclave and seal it, and crystallize at a constant temperature of 125°C for 8 hours. After the crystallization is complete, the product Centrifuge, wash with 80°C distilled water until the pH value remains unchanged, dry at 100°C, and calcinate in a muffle furnace at 450°C for 4 hours to obtain Ru-Pr isomorphously substituted SAPO-11.

[0057] (2) Organic amine modification: The molar rati...