Catalyst for catalytically synthesizing aliphatic amine as well as preparation method and application of catalyst

Abstract

The invention discloses a catalyst for catalytic synthesis of aliphatic amine as well as a preparation method and application of the catalyst. According to the preparation method, alcohol and ammonia gas or ketone, hydrogen and ammonia gas are used as raw materials and react in the presence of a catalyst to generate the aliphatic amine, the aliphatic amine is C2-C6 saturated aliphatic amine, and the catalyst comprises a molecular sieve carrier and an active metal component fixed in a crystal structure of the molecular sieve carrier; the reaction for preparing the catalyst is carried out in the presence of a template agent, and the template agent is target aliphatic amine. According to the preparation method, high selectivity of a single target amine product can be realized, and reaction activity such as reaction selectivity can be kept for a long time without reduction.

Description

Technical Field

[0001] The invention relates to a catalyst for catalytically synthesizing fatty amines, a preparation method and application thereof. Background Art

[0002] Fatty amines are organic derivatives of ammonia, a type of organic amine, and are important synthetic raw materials for many chemical products. They are widely used in the fields of pesticides, medicines, dyes, etc. When synthesizing fatty amines industrially, alcohols or ketones are usually used as production raw materials. It is generally believed that the reaction mechanism is that alcohols are dehydrogenated to form carbonyl groups, or the carbonyl groups in ketone compounds react with ammonia to form imines, and then the imines are hydrogenated to form fatty amines.

[0003] In the prior art, a catalyst is usually added when synthesizing fatty amines. The catalyst is usually a cobalt-based or nickel-based catalyst, and is usually prepared by an impregnation method or a coprecipitation method. Although the selectivity of the target product of the fatty amine synthesis reaction can be adjusted by regulating the raw material composition of the catalyst, a variety of fatty amines are usually generated during the reaction, such as primary amines, secondary amines or tertiary amines, and the content of each amine is usually not low, that is, the selectivity of the single target amine product of the reaction is low, and it is difficult to obtain only a specific single type of amine target product, and it is difficult to achieve the industrialization of a single fatty amine target product.

[0004] A patent discloses the use of nickel-aluminum compounds as catalysts to prepare fatty amines by amination of alcohols in a fixed bed reactor under hydrogen conditions. However, the products contain primary amines, secondary amines, tertiary amines, nitriles and unreacted alcohols. The excessive number of product types makes subsequent separation and purification steps difficult. That is, using this catalyst, it is difficult to obtain a single target amine product, the target amine product is difficult to separate, and the reaction selectivity of the specific target amine product is low.

[0005] In addition, during the use of the catalyst, the active metal components are prone to agglomeration and sintering, which will lead to the stability of the catalyst, that is, the catalytic activity is reduced after long-term operation, that is, the catalyst life is not long enough.

[0006] It is difficult for the catalysts in the prior art to simultaneously achieve high selectivity for a specific single target amine product when catalyzing the synthesis of fatty amines, and high catalyst stability, so as to maintain the catalytic activity for a long time without reduction. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide an improved method for preparing fatty amines in view of the shortcomings and deficiencies of the prior art, wherein the method can achieve high selectivity of a single target amine product, and the reaction activity, such as reaction selectivity, can be maintained for a long time without decreasing.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] A method for preparing a fatty amine comprises taking alcohol and ammonia, or ketone, hydrogen and ammonia as raw materials, reacting in the presence of a catalyst to generate the fatty amine, wherein the fatty amine is a C2-C6 saturated fatty amine, and the catalyst comprises a molecular sieve carrier and an active metal component fixed inside the crystal structure of the molecular sieve carrier; the reaction for preparing the catalyst is carried out in the presence of a template, and the template is a target fatty amine.

[0010] In some embodiments, the fatty amine is selected from one or more combinations of monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, mono-n-propylamine, mono-n-butylamine, and di-n-butylamine.

[0011] In some embodiments, the catalyst is prepared from raw materials in the presence of a template by hydrothermal synthesis, solid phase synthesis, microwave synthesis or sol-gel synthesis.

[0012] The hydrothermal synthesis method, for example, may be synthesizing the material by heating it in an oven in a system containing water; the solid phase synthesis method, for example, may be mixing the material by grinding and synthesizing it without adding additional water; the microwave synthesis method, for example, may be synthesizing the material by microwave heating in a system containing water.

[0013] In some embodiments, the molecular sieve carrier is selected from a combination of one or more of ZSM-5, Beta, SAPO-34, SAPO-11, and SAPO-41 molecular sieves.

[0014] In some embodiments, the catalyst includes, by mass percentage, 10%-25% of active metal components and 75%-90% of molecular sieve carrier.

[0015] In some embodiments, the active metal component is selected from a combination of one or more of Ni, Co, Cu, Pt, Pd, and Re.

[0016] In some embodiments, the active metal component is selected from Ni or Co or Cu or a combination of Co and Ni or a combination of Ni and Pt.

[0017] In some embodiments, when the active metal component contains Ni, Co or Cu, the mass percentage of Ni, Co or Cu in the catalyst is 10%-21%.

[0018] In some embodiments, when the active metal component contains Pt, Pd or Re, the mass percentage of Pt, Pd or Re in the catalyst is 0.5%-5%.

[0019] In some embodiments, the catalyst is prepared by a preparation method comprising the following steps: 1) loading active metal oxide on a support by impregnation or hydrolysis to obtain active metal oxide / support; 2) subjecting a silicon source, an aluminum source, an alkali source, the template, and the active metal oxide / support to hydrothermal reaction, filtering, and calcining to obtain a catalyst precursor; 3) subjecting the catalyst precursor to reduction reaction using a reducing agent to obtain the catalyst; the support is selected from silicon oxide or silica-alumina gel. The above support is one of the raw materials for synthesizing a molecular sieve carrier.

[0020] In some embodiments, the catalyst is prepared by a preparation method comprising the following steps: 1) loading active metal oxide on a molecular sieve support by an impregnation method to obtain an active metal oxide / molecular sieve support; 2) subjecting the template, the active metal oxide / molecular sieve support, and an optional silicon source, an optional aluminum source, and an optional phosphorus source to a hydrothermal reaction, filtering, and calcining to obtain a catalyst precursor; 3) subjecting the catalyst precursor to a reduction reaction using a reducing agent to obtain the catalyst; the molecular sieve support and the molecular sieve carrier are of the same or different types. The above-mentioned molecular sieve support is also a molecular sieve, but in a subsequent molecular sieve carrier synthesis reaction, a molecular sieve carrier is generated in situ or formed by crystallization. The molecular sieve support may be a molecular sieve crystal that is the same as the molecular sieve carrier of the catalyst (equivalent to a seed crystal at this time), or a molecular sieve crystal that is different from the molecular sieve carrier of the catalyst; when the molecular sieve support and the molecular sieve carrier of the catalyst are of different types, they grow by crystallization.

[0021] In some embodiments, the silicon source is selected from one or more combinations of silica sol, white carbon black, silica gel, and sodium silicate.

[0022] In some embodiments, the aluminum source is selected from a combination of one or more of aluminum hydroxide, pseudo-boehmite, aluminum oxide, and aluminum isopropoxide.

[0023] In some embodiments, the alkaline source is sodium hydroxide.

[0024] In some embodiments, the phosphorus source is selected from phosphoric acid, ammonium hydrogen phosphate, or a combination of one or more thereof.

[0025] In some embodiments, during the impregnation method, the water-soluble salt solution of the active metal component is impregnated into silicon oxide or silica-alumina colloid, and after the impregnation, the solid obtained after the impregnation is calcined to obtain the active metal oxide / support. The impregnation method can be an equal volume impregnation method.

[0026] In some embodiments, during the hydrolysis method, a water-soluble salt solution of the active metal component is reacted with tetraalkoxysilane to remove water to obtain a solid, which is then calcined to obtain an active metal oxide / support.

[0027] In some embodiments, the molar ratio of the total amount of silicon in the silicon source and active metal oxide / support, aluminum in the aluminum source, alkali source, and template is 1:0.005-0.02:0.05-0.12:0.13-0.67, preferably 1:0.01:0.05-0.12:0.13-0.67.

[0028] In some embodiments, the molecular sieve support is selected from SAPO-34, SAPO-11 or SAPO-41, the molecular sieve carrier is selected from SAPO-34, SAPO-11 or SAPO-41, the molecular sieve support and the molecular sieve carrier are of the same type, and in step 2), the raw materials for the hydrothermal reaction include a silicon source, an aluminum source and a phosphorus source.

[0029] In some embodiments, the molar ratio of silicon in the silicon source, aluminum in the aluminum source, phosphorus in the phosphorus source, and the template is 0.4-0.6:1:1:1-3; the mass ratio of the active metal oxide / molecular sieve support and the aluminum source in terms of alumina is 1-2:1.

[0030] In some embodiments, the molecular sieve support is a Y molecular sieve, the molecular sieve carrier is a ZSM-5 molecular sieve, the molecular sieve support and the molecular sieve carrier are of different types, and in step 2), no silicon source, no aluminum source, and no phosphorus source are added during the hydrothermal reaction. The Y molecular sieve forms a ZSM-5 molecular sieve by crystallization.

[0031] In some embodiments, the temperature of the hydrothermal reaction is 100-200°C.

[0032] In some embodiments, the calcination temperature is 400-600°C.

[0033] In some embodiments, the reducing agent is hydrogen.

[0034] In some embodiments, the reduction reaction temperature is 400-600°C.

[0035] In some embodiments, the mass space velocity of the alcohol or ketone is 0.4-3h -1 .

[0036] In some embodiments, when the reaction raw materials are alcohol and ammonia, the reaction is carried out in a hydrogen atmosphere.

[0037] In some embodiments, the molar ratio of the alcohol or ketone to hydrogen is 1:1-4.

[0038] In some embodiments, the molar ratio of the alcohol or ketone to ammonia is 1:1-4.

[0039] In some embodiments, the reaction temperature is 140-185°C.

[0040] In some embodiments, the reaction pressure is 0.4-0.6 MPa.

[0041] The present invention also provides the above catalyst.

[0042] Compared with the prior art, the present invention has the following advantages:

[0043] The synthesis method of the present invention uses a coated metal@molecular sieve catalyst having a topological structure associated with the target fatty amine to be synthesized, and the catalyst can synthesize the corresponding target single specific fatty amine product with high selectivity.

[0044] When preparing the catalyst of the present invention, the synthesized target fatty amine molecule is used as an organic template. Through the interaction between the target fatty amine molecule and the formed catalyst carrier molecular sieve framework, the molecular sieve material with the lowest binding energy with the specific target fatty amine is screened out as the catalyst carrier, thereby making the catalyst material have significantly improved reaction selectivity for the target fatty amine, and a single target fatty amine can be obtained with high selectivity, and the post-processing is very simple.

[0045] The active metal components of the catalyst of the present invention are fixed inside the structure of the molecular sieve carrier, so the active components have good anti-sintering performance, the catalyst has good stability, the active metal components are not prone to metal migration and agglomeration, and the catalytic activity can be maintained without reduction during long-term operation.

[0046] The synthesis method of the invention can achieve an alcohol or ketone conversion rate of more than 99%, a target fatty amine selectivity of more than 90.0%, and the catalytic activity of the catalyst is substantially not reduced after the catalyst is operated for more than 1000 hours. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 This is the XRD spectrum of the catalyst prepared in Example 2;

[0048] Figure 2 This is the XRD spectrum of the catalyst prepared in Example 4;

[0049] Figure 3 This is the XRD spectrum of the catalyst prepared in Example 6. DETAILED DESCRIPTION

[0050] The present invention is further described below in conjunction with the examples. However, the present invention is not limited to the following examples. The implementation conditions used in the examples can be further adjusted according to the different requirements of specific use, and the implementation conditions not specified are conventional conditions in the industry. The technical features involved in each embodiment of the present invention can be combined with each other as long as they do not conflict with each other.

[0051] In the present invention, metal component / carrier refers to the carrier directly loading the metal component by impregnation or the like, and the metal component is usually located on the surface of the carrier, for example, Co3O4-NiO / ZSM-5 means Co3O4-NiO is located on the surface of ZSM-5; and metal component@carrier refers to the carrier fixing and coating the metal component, and the metal component is usually located inside the crystal structure of the carrier, for example, CoNi@ZSM-5 means CoNi is located inside the ZSM-5 structure.

[0052] The coated metal@molecular sieve catalyst of the present invention fixes the active metal inside the crystal structure of the molecular sieve material, stabilizes the active components, prevents the catalyst from high-temperature sintering during the reaction, and improves the stability of the catalyst.

[0053] Example 1

[0054] This embodiment provides a catalyst using mono-n-butylamine as a template, and uses it to catalyze the synthesis of mono-n-butylamine, as follows:

[0055] 1) Preparation of Co3O4 / SiO2:

[0056] The same volume of white carbon black is impregnated in an aqueous solution containing cobalt nitrate by an equal volume impregnation method. After the impregnation, the powder is dried and calcined to prepare Co3O4 / SiO2. The equal volume impregnation means that after the white carbon black is added to the aqueous solution, the aqueous solution just covers the white carbon black.

[0057] 2) Preparation of molecular sieve catalyst:

[0058] Sodium hydroxide, sodium aluminate NaAlO2, Co3O4 / SiO2, white carbon black and monobutylamine are added to water and stirred evenly, wherein the molar ratio of NaOH:SiO2 (the total amount of SiO2 in Co3O4 / SiO2 and white carbon black):NaAlO2:monobutylamine:water is 0.05:1:0.01:0.13:15. After stirring evenly, put it into a polytetrafluoroethylene-lined reactor, and the sealed reactor is crystallized at 160°C for 48h. After the reaction is completed, the solid is washed with deionized water until the pH of the filtered water reaches 7 to obtain monobutylamine-Co3O4@ZSM-5. The filtered solid is calcined at 550°C for 4h to obtain Na-Co3O4@ZSM-5. The prepared Na-Co3O4@ZSM-5 was added to a 1.0 mol / L NH4Cl aqueous solution at a solid-liquid ratio of 1:50, and fully exchanged at 60°C for 3 times, each time for 6 hours. + -Co3O4@ZSM-5 was calcined at 500℃ for 2h to prepare H + -Co3O4@ZSM-5. Finally, H + -Co3O4@ZSM-5 was reduced at 500°C for 6 hours in a hydrogen atmosphere to obtain a reduced catalyst Co@ZSM-5. The mass percentage of Co in the catalyst was 16% as measured by ICP.

[0059] 3) Catalyst evaluation, synthesis reaction:

[0060] The prepared catalyst was granulated into 20-40 meshes, and 4g of the catalyst was placed in a catalyst evaluation device. The raw material was n-butanol. Then, the raw material n-butanol was fed at a mass space velocity of 0.4 / h, a molar ratio of hydrogen: n-butanol = 3, ammonia: n-butanol = 3, a reaction temperature of 175°C, and a reaction pressure of 0.4MPa for testing. The test results showed that the n-butanol conversion rate was 99.5%, and the mono-n-butylamine selectivity was 90.2%. Catalyst performance after running for 1000h: n-butanol conversion rate was 99.0%, and the mono-n-butylamine selectivity was 91.2%.

[0061] Example 2

[0062] This embodiment provides a catalyst using monoisopropylamine as a template, and uses the catalyst to catalyze the synthesis of monoisopropylamine, as follows:

[0063] 1) Preparation of NiO / SiO2:

[0064] Tetraethoxysilane is added to a nickel nitrate aqueous solution by a hydrolysis method. After sufficient stirring, the water is continuously evaporated, and the solid obtained after evaporation is calcined to obtain NiO / SiO2.

[0065] 2) Preparation of molecular sieve catalyst:

[0066] Sodium hydroxide, sodium aluminate, fine silica gel, NiO / SiO2 and monoisopropylamine were added to water and stirred evenly, wherein the molar ratio of NaOH:SiO2 (the total amount of SiO2 in NiO / SiO2 and fine silica gel):NaAlO2:monoisopropylamine:water was 0.12:1:0.01:0.67:32. After stirring evenly, it was placed in a polytetrafluoroethylene-lined reactor, and the sealed reactor was crystallized at 170°C for 48 hours. After the reaction was completed, the solid was washed with deionized water until the pH of the filtered water reached 7 to obtain monoisopropylamine-NiO@ZSM-5. The filtered solid was calcined at 550°C for 4 hours to obtain Na-NiO@ZSM-5. The prepared Na-NiO@ZSM-5 was added to a 1.0 mol / L NH4Cl aqueous solution at a solid-liquid ratio of 1:50, and fully exchanged 3 times at 60°C, each exchange for 6 hours. Then the NH4 + -NiO@ZSM-5 was calcined at 500 °C for 2 h to prepare H + -NiO@ZSM-5. Finally, H + -NiO@ZSM-5 was reduced at 500°C for 6 hours in a hydrogen atmosphere to obtain a reduced catalyst Ni@ZSM-5. The mass percentage of Ni in the catalyst was 14% as measured by ICP.

[0067] 3) Catalyst evaluation, synthesis reaction:

[0068] The prepared catalyst was granulated into 20-40 meshes, and 4g of the catalyst was placed in a catalyst evaluation device. The raw material was acetone, and then the raw material acetone was fed according to the mass space velocity of 1 / h, the molar ratio of hydrogen: acetone = 2, ammonia: acetone = 4, the reaction temperature was 140°C, and the reaction pressure was 0.4MPa for testing. The test results showed that the acetone conversion rate was 99.7%, and the monoisopropylamine selectivity was 96.1%. After running for 1000h, the catalyst performance: acetone conversion rate was 98.7%, and monoisopropylamine selectivity was 96.2%.

[0069] Example 3

[0070] The present embodiment provides a catalyst using triethylamine as a template, and uses it to catalyze the synthesis of triethylamine, as follows:

[0071] 1) Preparation of CuO / SAPO-34:

[0072] The SAPO-34 molecular sieve is impregnated in an aqueous solution containing copper nitrate in equal volumes by an equal volume impregnation method. After the impregnation is completed, the powder is dried and calcined to prepare CuO / SAPO-34.

[0073] 2) Preparation of Cu@SAPO-34 catalyst:

[0074] Pseudo-boehmite, fine silica gel and phosphoric acid were used as aluminum source, silicon source and phosphorus source respectively, triethylamine (TEA) was used as template, and the aluminum source and phosphorus source were mixed with deionized water at a molar ratio of P:Al:Si:TEA:H2O=1:1:0.6:3:50 and stirred thoroughly. The measured template was added dropwise, and the silicon source was added after stirring thoroughly. The stirring was continued until a uniform gel was formed, and then 100% CuO / SAPO-34 molecular sieve was added by weight of alumina. After stirring evenly, it was transferred into a stainless steel synthesis reactor with a 100mL polytetrafluoroethylene liner, and heated to 200℃ in a sealed manner, and crystallized under its own pressure for 24h. After the reaction was completed, the solid was washed with deionized water until the pH of the filtered water reached 7 to obtain triethylamine-CuO@SAPO-34. The filtered solid was calcined at 550℃ for 4h to obtain CuO@SAPO-34. Finally, the CuO@SAPO-34 was reduced at 500°C for 6 h in a hydrogen atmosphere to obtain the reduced catalyst Cu@SAPO-34. The mass content of Cu was measured by ICP to be 20%.

[0075] 3) Catalyst evaluation, synthesis reaction:

[0076] The prepared catalyst was granulated into 20-40 meshes, and 4g of the catalyst was placed in a catalyst evaluation device. The raw material was ethanol. Then, the raw material mass space velocity was 0.5 / h, the molar ratio of hydrogen: ethanol = 1, ammonia: ethanol = 1 was fed, the reaction temperature was 175°C, and the reaction pressure was 0.4MPa for testing. The test results showed that the ethanol conversion rate was 99.4%, and the triethylamine selectivity was 99.1%. After running for 1000h, the catalyst performance: ethanol conversion rate was 98.9%, and triethylamine selectivity was 98.5%.

[0077] Example 4

[0078] This embodiment provides a catalyst using diisopropylamine as a template, and uses it to catalyze the synthesis of diisopropylamine, as follows:

[0079] 1) Preparation of Co3O4-NiO / SAPO-11:

[0080] The SAPO-11 molecular sieve is impregnated in an aqueous solution containing cobalt nitrate and nickel nitrate in equal volumes by an equal volume impregnation method. After the impregnation, the powder is dried and calcined to prepare Co3O4-NiO / SAPO-11.

[0081] 2) Preparation of CoNi@SAPO-11 catalyst:

[0082] Pseudo-boehmite, fine silica gel and phosphoric acid were used as aluminum source, silicon source and phosphorus source respectively, diisopropylamine (DIPA) was used as template, and the aluminum source and phosphorus source were mixed with deionized water at a molar ratio of P:Al:Si:DIPA:H2O=1:1:0.4:1:28 and stirred thoroughly. The measured template was added dropwise, and the silicon source was added after stirring thoroughly. The stirring was continued until a uniform gel was formed, and then 100% Co3O4-NiO / SAPO-11 molecular sieve was added based on the mass of alumina. After stirring evenly, it was transferred into a stainless steel synthesis reactor with a 100mL polytetrafluoroethylene liner, and heated to 190°C in a sealed manner, and crystallized for 24h under its own pressure. After the reaction was completed, the solid was washed with deionized water until the pH of the filtered water reached 7 to obtain diisopropylamine-Co3O4-NiO@SAPO-11. The filtered solid was calcined at 550°C for 4h to obtain Co3O4-NiO@SAPO-1. Finally, Co3O4-NiO@SAPO-11 was reduced at 500°C for 6h in a hydrogen atmosphere to obtain the reduced catalyst CoNi@SAPO-11. The mass content of Cu and Ni was measured by ICP to be 15% and 15% respectively.

[0083] 3) Catalyst evaluation, synthesis reaction:

[0084] The prepared catalyst was granulated into 20-40 meshes, and 4g of the catalyst was placed in a catalyst evaluation device. The raw material was acetone. Then, the raw material mass space velocity was 1 / h, the molar ratio of hydrogen: acetone = 4, ammonia: acetone = 1 was fed, the reaction temperature was 165°C, and the reaction pressure was 0.6MPa for testing. The test results showed that the acetone conversion rate was 99.6%, and the diisopropylamine selectivity was 91.2%. After running for 1000h, the catalyst performance: acetone conversion rate was 99.3%, and diisopropylamine selectivity was 90.2%.

[0085] Example 5

[0086] This embodiment provides a catalyst using di-n-butylamine as a template, and uses it to catalyze the synthesis of di-n-butylamine, as follows:

[0087] 1) Preparation of Co3O4-CuO / SAPO-41:

[0088] The SAPO-41 molecular sieve is impregnated in an aqueous solution containing cobalt nitrate and copper nitrate in equal volumes by an equal volume impregnation method. After the impregnation, the powder is dried and calcined to prepare Co3O4-CuO / SAPO-41.

[0089] 2) Preparation of CoCu@SAPO-41 catalyst:

[0090] Pseudo-boehmite, silica sol (aqueous solution with a mass percentage concentration of 30%) and phosphoric acid were used as aluminum source, silicon source and phosphorus source respectively, dibutylamine (DBA) was used as template, and the aluminum source and phosphorus source were mixed with deionized water at a molar ratio of P:Al:Si:DBA:H2O=1:1:0.6:2:55 and stirred thoroughly, and the measured template was added dropwise, and the silicon source was added after stirring thoroughly, and stirring was continued until a uniform gel was formed, and then 100% Co3O4-CuO / SAPO-41 molecular sieve was added based on the mass of alumina, and after stirring uniformly, it was transferred into a stainless steel synthesis reactor with a 100mL polytetrafluoroethylene liner, and heated to 180°C in a sealed manner, and crystallized for 48h under its own pressure. After the reaction was completed, the solid was washed with deionized water until the pH of the filtered water reached 7, and dibutylamine-Co3O4-CuO@SAPO-41 was obtained. The filtered solid was calcined at 550°C for 4 hours to obtain Co3O4-CuO@SAPO-41. Finally, Co3O4-CuO@SAPO-41 was reduced at 500°C for 6 hours in a hydrogen atmosphere to obtain the reduced catalyst CoCu@SAPO-41. The mass content of Co was 11% and the mass content of Cu was 10% as measured by ICP.

[0091] 3) Catalyst evaluation, synthesis reaction:

[0092] The prepared catalyst was granulated into 20-40 mesh, and 4g of the catalyst was placed in a catalyst evaluation device. The raw material was n-butanol. Then, the raw material mass space velocity was 0.4 / h, the molar ratio of hydrogen: n-butanol = 1, ammonia: n-butanol = 1.5 was fed, the reaction temperature was 175°C, and the reaction pressure was 0.4MPa for testing. The test results showed that the n-butanol conversion rate was 99.5%, and the di-n-butylamine selectivity was 93.8%. Catalyst performance after running for 1000h: n-butanol conversion rate was 98.5%, and di-n-butylamine selectivity was 93.0%.

[0093] Example 6

[0094] The present embodiment provides a catalyst using diethylamine as a template, and uses it to catalyze the synthesis of diethylamine, as follows:

[0095] 1) Preparation of CuO-NiO / SAPO-34:

[0096] The SAPO-34 molecular sieve is impregnated in an aqueous solution containing copper nitrate and nickel nitrate in equal volumes by an equal volume impregnation method. After the impregnation, the powder is dried and calcined to prepare CuO-NiO / SAPO-34.

[0097] 2) Preparation of CuNi@SAPO-34 catalyst:

[0098] Pseudo-boehmite, fine silica gel and phosphoric acid were used as aluminum source, silicon source and phosphorus source respectively, diethylamine (DEA) was used as template, and the aluminum source and phosphorus source were mixed with deionized water at a molar ratio of P:Al:Si:DEA:H2O=1:1:0.4:3:50 and stirred thoroughly, and the measured template was added dropwise, and the silicon source was added after stirring thoroughly, and the stirring was continued until a uniform gel was formed, and then 100% CuO-NiO / SAPO-34 molecular sieve was added based on the mass of alumina, and after stirring evenly, it was transferred into a stainless steel synthesis reactor with a 100mL polytetrafluoroethylene liner, and heated to 200℃ in a sealed manner, and crystallized for 60h under its own pressure. After the reaction was completed, the solid was washed with deionized water until the pH of the filtered water reached 7, and diethylamine-CuO-NiO@SAPO-34 was obtained. The filtered solid was calcined at 550℃ for 4h to obtain CuO-NiO@SAPO-34. Finally, the CuO-NiO@SAPO-34 was reduced at 500°C for 6 h in a hydrogen atmosphere to obtain the reduced catalyst CuNi@SAPO-34. The mass content of Cu and the mass content of Ni were measured by ICP to be 11% and 12%.

[0099] 3) Catalyst evaluation, synthesis reaction:

[0100] The prepared catalyst was granulated into 20-40 meshes, and 4g of the catalyst was placed in a catalyst evaluation device. The raw material was ethanol. Then, the raw material mass space velocity was 0.5 / h, the molar ratio of hydrogen: ethanol = 1.5, and the ammonia: ethanol = 1.5 was fed, the reaction temperature was 175°C, and the reaction pressure was 0.5MPa for testing. The test results showed that the ethanol conversion rate was 99.6%, and the diethylamine selectivity was 90.4%. After running for 1000h, the catalyst performance: ethanol conversion rate 99.2%, diethylamine selectivity 90.0%.

[0101] Example 7

[0102] This embodiment provides a catalyst using mono-n-propylamine as a template, and uses the catalyst to catalyze the synthesis of mono-n-propylamine, as follows:

[0103] 1) Preparation of NiO-PtO2 / Y:

[0104] By an equal volume impregnation method, an equal volume of Y molecular sieve (silicon to aluminum molar ratio is 100) is impregnated in an aqueous solution containing nickel nitrate and chloroplatinic acid. After the impregnation is completed, the powder is dried and calcined to prepare NiO-PtO2 / Y.

[0105] 2) Preparation of NiPt@ZSM-5 catalyst:

[0106] NiO-PtO2 / Y, mono-n-propylamine and water were added into a mortar at a molar ratio of SiO2:PA:H2O=1:1:4 for grinding. After grinding for 30 minutes, 5% ZSM-5 molecular sieve of NiO-PtO2 / Y was added as a seed crystal, and then transferred into a stainless steel synthesis reactor with a 100mL polytetrafluoroethylene liner, and heated to 180°C in a sealed manner, and crystallized for 48 hours under its own pressure. After the reaction, the solid was washed with deionized water until the pH of the filtered water reached 7 to obtain mono-n-propylamine-NiO-PtO2@ZSM-5. The filtered solid was calcined at 550°C for 4 hours to obtain NiO-PtO2@ZSM-5. Finally, NiO-PtO2@ZSM-5 was reduced at 500°C for 6 hours in a hydrogen atmosphere to obtain the reduced catalyst NiPt@ZSM-5. The mass content of Ni and the mass content of Pt were measured by ICP to be 21% and 1% respectively.

[0107] 3) Catalyst evaluation, synthesis reaction:

[0108] The prepared catalyst was granulated into 20-40 meshes, and 4g of the catalyst was placed in a catalyst evaluation device. The raw material was n-propanol. Then, the raw material mass space velocity was 0.5 / h, the molar ratio of hydrogen: ethanol = 1.5, ammonia: ethanol = 4 was fed, the reaction temperature was 185°C, and the reaction pressure was 0.4MPa for testing. The test results showed that the n-propanol conversion rate was 99.5%, and the mono-n-propylamine selectivity was 98.0%. Catalyst performance after running for 1000h: n-propanol conversion rate was 99.2%, and the mono-n-propylamine selectivity was 98.2%.

[0109] Comparative Example 1

[0110] According to the catalyst in Example 1 of patent CN104262165A, Cu:Ni:Cr:SBA-15=8:1:4:87.

[0111] Catalyst Evaluation:

[0112] Same as Example 1: The prepared catalyst was granulated into 20-40 mesh, and 4g of the catalyst was placed in a catalyst evaluation device. The raw material was n-butanol. Then, the raw material mass space velocity was 0.4 / h, the molar ratio of hydrogen: n-butanol = 3, ammonia: n-butanol = 3 was fed, the reaction temperature was 175°C, and the reaction pressure was 0.4MPa for testing. The test results showed that the n-butanol conversion rate was 99.2%, among which the selectivity of mono-n-butylamine was 23.7%, the selectivity of di-n-butylamine was 51.5%, and the selectivity of tri-n-butylamine was 24%. It can be seen that it is difficult to obtain a single specific target fatty amine.

[0113] Comparative Example 2

[0114] This comparative example provides a catalyst (without fixing the active component first), and uses it to catalyze the synthesis of mono-n-butylamine, as follows:

[0115] 1) Preparation of molecular sieve carrier containing target amine template:

[0116] Sodium hydroxide, sodium aluminate NaAlO2, SiO2 and mono-n-butylamine are added to water and stirred evenly, wherein the molar ratio of NaOH: SiO2: NaAlO2: mono-n-butylamine: water is 0.05:1:0.01:0.13:15. After stirring evenly, it is placed in a polytetrafluoroethylene-lined reactor, and the sealed reactor is crystallized at 160°C for 48 hours. After the reaction is completed, the solid is washed with deionized water until the pH of the filtered water reaches 7 to obtain mono-n-butylamine / ZSM-5. The filtered solid is calcined at 550°C for 4 hours to obtain Na-ZSM-5. The prepared Na-ZSM-5 is added to a 1.0 mol / L NH4Cl aqueous solution at a solid-liquid ratio of 1:50, and fully exchanged 3 times at 60°C, each exchange for 6 hours. Then the NH4 obtained after ion exchange is + -ZSM-5 was calcined at 500 °C for 2 h to prepare H + -ZSM-5.

[0117] 2) Preparation of Co / ZSM-5 catalyst:

[0118] By means of equal volume impregnation, H + -ZSM-5 molecular sieve is dispersed in an aqueous solution containing cobalt nitrate. After the impregnation, the powder obtained after the impregnation is dried and reduced at 500°C for 6 hours in a hydrogen atmosphere to obtain a Co / ZSM-5 catalyst. The mass percentage of Co in the catalyst is 16%.

[0119] Catalyst Evaluation:

[0120] Same as Example 1: Test results: n-butanol conversion rate is 98.5%, wherein the selectivity of mono-n-butylamine is 55.4%, the selectivity of di-n-butylamine is 25.5%, and the selectivity of tri-n-butylamine is 18.9%. After running for 600 hours, the conversion rate of n-butanol is 60.9%.

[0121] Comparative Example 3

[0122] This comparative example provides a catalyst (without using the target amine as a template), and uses it to catalyze the synthesis of mono-n-butylamine, as follows:

[0123] 1) Preparation of Co3O4 / SiO2:

[0124] The same volume of white carbon black is impregnated in an aqueous solution containing cobalt nitrate by an equal volume impregnation method, wherein the mass of the Co element is 30% of the mass of the white carbon black. After the impregnation, the powder is dried and calcined to prepare Co3O4 / SiO2. The equal volume impregnation means that after the white carbon black is added to the aqueous solution, the aqueous solution just covers the white carbon black.

[0125] 2) Preparation of molecular sieve catalyst:

[0126] Sodium hydroxide, sodium aluminate NaAlO2, Co3O4 / SiO2 and tetrapropylammonium hydroxide TPAOH (aqueous solution with a mass percentage concentration of 35%) were added to water and stirred evenly, wherein the molar ratio of NaOH: SiO2: NaAlO2: TPAOH: water was 0.05:1:0.01:0.13:15. After stirring evenly, it was placed in a polytetrafluoroethylene-lined reactor, and the sealed reactor was crystallized at 160°C for 48 hours. After the reaction was completed, the solid was washed with deionized water until the pH of the filtered water reached 7 to obtain Co3O4@ZSM-5. The filtered solid was calcined at 550°C for 4 hours to obtain Na-Co3O4@ZSM-5. The prepared Na-Co3O4@ZSM-5 was added to a 1.0 mol / L NH4Cl aqueous solution at a solid-liquid ratio of 1:50, and fully exchanged 3 times at 60°C, each exchange for 6 hours. Then the NH4 + -Co3O4@ZSM-5 was calcined at 500℃ for 2h to prepare H + -Co3O4@ZSM-5. Finally, H + -Co3O4@ZSM-5 was reduced at 500°C for 6 hours in a hydrogen atmosphere to obtain a reduced catalyst Co@ZSM-5. The mass percentage of Co in the catalyst was 16% as measured by ICP.

[0127] 3) Catalyst evaluation:

[0128] Same as Example 1: Test results showed that the conversion rate of n-butanol was 98.9%, wherein the selectivity of mono-n-butylamine was 25.6%, the selectivity of di-n-butylamine was 50.9%, and the selectivity of tri-n-butylamine was 23.4%.

[0129] It can be seen that when preparing a catalyst, if the active components are not fixed first and then the molecular sieve is synthesized in situ, the active components are prone to sintering, the stability of the catalyst is significantly reduced, and the catalytic activity is reduced after long-term operation. If a specific single type of fatty amine is not used as a template for the synthesis of the catalyst, it is difficult to achieve a high reaction selectivity of a specific single type of fatty amine when synthesizing the fatty amine. However, the present application uses the target fatty amine as a template when preparing the catalyst, which can make the catalyst more applicable and select the target product, and significantly improve the reaction selectivity of the target fatty amine.

[0130] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

[0131] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

Claims

1. A method for preparing a fatty amine, wherein alcohol and ammonia, or ketone, hydrogen and ammonia are used as raw materials, and react in the presence of a catalyst to generate the fatty amine, wherein the fatty amine is a C2-C6 saturated fatty amine, and is characterized in that: The catalyst comprises a molecular sieve carrier and an active metal component fixed inside the crystal structure of the molecular sieve carrier; the reaction for preparing the catalyst is carried out in the presence of a template agent, and the template agent is a target fatty amine.

2. The method for preparing fatty amine according to claim 1, characterized in that: The fatty amine is selected from one or more combinations of monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, mono-n-propylamine, mono-n-butylamine and di-n-butylamine.

3. The method for preparing fatty amine according to claim 1, characterized in that: The catalyst is prepared from raw materials in the presence of a template agent through a hydrothermal synthesis method, a solid phase synthesis method, a microwave synthesis method or a sol-gel synthesis method.

4. The method for preparing fatty amine according to claim 1, characterized in that: The molecular sieve carrier is selected from one or more combinations of ZSM-5, Beta, SAPO-34, SAPO-11, and SAPO-41 molecular sieves.

5. The method for preparing fatty amine according to claim 1, characterized in that: In terms of mass percentage, the catalyst comprises 10%-25% of active metal components and 75%-90% of molecular sieve carriers.

6. The method for preparing fatty amine according to claim 1, characterized in that: The active metal component is selected from one or more combinations of Ni, Co, Cu, Pt, Pd and Re.

7. The method for preparing fatty amine according to claim 1, characterized in that: The active metal component is selected from Ni or Co or Cu or a combination of Co and Ni or a combination of Ni and Pt.

8. The method for preparing fatty amine according to claim 7, characterized in that: When the active metal component contains Ni, Co or Cu, the mass percentage of Ni, Co or Cu in the catalyst is 10%-21%; when the active metal component contains Pt, Pd or Re, the mass percentage of Pt, Pd or Re in the catalyst is 0.5%-5%.

9. The method for preparing fatty amine according to claim 1, characterized in that: The catalyst is The preparation method comprises the following steps: 1) loading active metal oxide on a support by an impregnation method or a hydrolysis method to obtain active metal oxide / support; 2) subjecting a silicon source, an aluminum source, an alkali source, the template agent, and the active metal oxide / support to a hydrothermal reaction, filtering, and calcining to obtain a catalyst precursor; 3) subjecting the catalyst precursor to a reduction reaction using a reducing agent to obtain the catalyst; The support is selected from silicon oxide or silica-alumina gel.

10. The method for preparing fatty amine according to claim 1, characterized in that: The catalyst is The preparation method comprises the following steps: 1) loading active metal oxide on a molecular sieve support by an impregnation method to obtain an active metal oxide / molecular sieve support; 2) subjecting the template, the active metal oxide / molecular sieve support, and an optional silicon source, an optional aluminum source, and an optional phosphorus source to a hydrothermal reaction, filtering, and calcining to obtain a catalyst precursor; 3) subjecting the catalyst precursor to a reduction reaction using a reducing agent to obtain the catalyst; the molecular sieve support and the molecular sieve carrier are of the same or different types.

11. The method for preparing fatty amine according to claim 9 or 10, characterized in that: The silicon source is selected from a combination of one or more of silica sol, white carbon black, silica gel, and sodium silicate; and / or, the aluminum source is selected from a combination of one or more of aluminum hydroxide, pseudo-boehmite, alumina, and aluminum isopropoxide; and / or, the alkali source is sodium hydroxide; and / or, the phosphorus source is selected from a combination of one or more of phosphoric acid and ammonium hydrogen phosphate.

12. The method for preparing fatty amine according to claim 9 or 10, characterized in that: In the impregnation method, a water-soluble salt solution of the active metal component is impregnated into silicon oxide or silica-alumina colloid, and after the impregnation, the solid obtained after the impregnation is calcined to obtain the active metal oxide / support.

13. The method for preparing fatty amine according to claim 9, characterized in that: In the hydrolysis method, a water-soluble salt solution of the active metal component is reacted with tetraalkoxysilane to remove water to obtain a solid, which is then calcined to obtain an active metal oxide / support.

14. The method for preparing fatty amine according to claim 9, characterized in that: The molar ratio of the total amount of silicon in the silicon source and active metal oxide / support, aluminum in the aluminum source, alkali source, and template agent is 1:0.005-0.02:0.05-0.12:0.13-0.

67.

15. The method for preparing fatty amine according to claim 10, characterized in that: The molecular sieve support is selected from SAPO-34, SAPO-11 or SAPO-41, the molecular sieve carrier is selected from SAPO-34, SAPO-11 or SAPO-41, the molecular sieve support and the molecular sieve carrier are of the same type, and in step 2), the raw materials for the hydrothermal reaction include a silicon source, an aluminum source and a phosphorus source.

16. The method for preparing fatty amine according to claim 15, characterized in that: The molar ratio of silicon in the silicon source, aluminum in the aluminum source, phosphorus in the phosphorus source, and the template is 0.4-0.6:1:1:1-3; the mass ratio of the active metal oxide / molecular sieve support and the aluminum source in terms of alumina is 1-2:

1.

17. The method for preparing fatty amine according to claim 10, characterized in that: The molecular sieve support is a Y molecular sieve, the molecular sieve carrier is a ZSM-5 molecular sieve, the molecular sieve support and the molecular sieve carrier are of different types, and in step 2), no silicon source, no aluminum source, and no phosphorus source are added during the hydrothermal reaction.

18. The method for preparing fatty amine according to claim 9 or 10, characterized in that: The temperature of the hydrothermal reaction is 100-200°C; and / or, the temperature of the calcination is 400-600°C; and / or, the reducing agent is hydrogen; and / or, the temperature of the reduction reaction is 400-600°C.

19. The method for preparing fatty amine according to claim 1, characterized in that: The mass space velocity of the alcohol or ketone is 0.4-3h -1 ; and / or, when the reaction raw materials are alcohol and ammonia, the reaction is carried out in a hydrogen atmosphere.

20. The method for preparing fatty amine according to claim 19, characterized in that: The molar ratio of the alcohol or ketone to hydrogen is 1:1-4; and / or the molar ratio of the alcohol or ketone to ammonia is 1:1-4.

21. The method for preparing fatty amine according to claim 1, characterized in that: The reaction temperature is 140-185° C.; and / or the reaction pressure is 0.4-0.6 MPa.

22. The catalyst of any one of claims 1 to 21.

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