CN114210361A - Catalyst for one-step synthesis of 6-aminocapronitrile from cyclohexanone oxime or caprolactam and preparation method thereof - Google Patents

Catalyst for one-step synthesis of 6-aminocapronitrile from cyclohexanone oxime or caprolactam and preparation method thereof Download PDF

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CN114210361A
CN114210361A CN202111611141.3A CN202111611141A CN114210361A CN 114210361 A CN114210361 A CN 114210361A CN 202111611141 A CN202111611141 A CN 202111611141A CN 114210361 A CN114210361 A CN 114210361A
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molecular sieve
aminocapronitrile
caprolactam
cyclohexanone oxime
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于向真
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal

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Abstract

The invention discloses a catalyst for synthesizing 6-aminocapronitrile from cyclohexanone oxime or caprolactam in one step and a preparation method thereof, wherein the catalyst uses a P-containing molecular sieve as an active component, the active component of the P-containing molecular sieve accounts for 10-80% by weight of a dry basis, a carrier accounts for 0-50% by weight of the active component, a binder accounts for 10-50% by weight of the active component, and the catalyst is microspheres with the shape of 1-300 micrometers or particles with the size of 0.5-10 mm. The preparation method comprises mixing molecular sieve and phosphorus-containing compound uniformly to obtain thick slurry, drying, and calcining to obtain solid powder to obtain P-containing molecular sieve; then mixing the P-containing molecular sieve with a carrier, deionized water and a binder, carrying out spray forming or extrusion molding, and then drying and roasting to prepare the catalyst. The catalyst has simple preparation process, is used for synthesizing 6-aminocapronitrile from cyclohexanone oxime or caprolactam serving as a raw material, has the advantages of high conversion rate, high yield and few byproducts, and the conversion rate of the cyclohexanone oxime or caprolactam can reach 99.0 percent, and the selectivity of the 6-aminocapronitrile can reach more than 95 percent.

Description

Catalyst for one-step synthesis of 6-aminocapronitrile from cyclohexanone oxime or caprolactam and preparation method thereof
Technical Field
The invention belongs to the field of petrochemical industry, and relates to a catalyst for synthesizing 6-aminocapronitrile from cyclohexanone oxime or caprolactam in one step and a preparation method thereof.
Background
Hexamethylenediamine is an important chemical and also a key raw material for synthesizing nylon 66, nylon 610, nylon 612 and the like, and is generally obtained by hydrogenation of hexamethylene dicyanide, hydrogenation of 6-aminocapronitrile or amination of caprolactam to 6-aminocapronitrile and hydrogenation, wherein 6-aminocapronitrile is an important intermediate product for synthesizing hexamethylenediamine.
Chinese patent CN113083270A provides a catalyst containing silicon oxide and aluminum oxide, a binder and the like are added to prepare a granular catalyst for a fixed bed, the granular catalyst is used for synthesizing caprolactam and 6-aminocapronitrile from cyclohexanone oxime, the reaction temperature is above 300 ℃, the conversion rate of cyclohexanone oxime can reach above 99%, 15% -19% of caprolactam is contained, the yield of a target product 6-aminocapronitrile reaches-80%, and the yield is low.
Chinese patent CN113413891A provides a catalyst composition containing one or more of alkaline earth metal oxide, transition metal oxide, silicon oxide, aluminum oxide and the like, and a binder and a peptizing agent are added to prepare a required shape, then the required shape is aged for 0.1-48 h at 5-50 ℃, dried for 10-64 h at 55-250 ℃, and roasted for 4-24 h at 400-950 ℃ to prepare the catalyst for preparing 6-aminocapronitrile from caprolactam, wherein the reaction temperature is more than 300 ℃, the conversion rate of the caprolactam can reach 90%, and the selectivity of the 6-aminocapronitrile reaches-99%.
Chinese patent 111992241a (a catalyst for synthesizing key intermediate of hexanediamine and its preparation method and use) proposes modifying molecular sieve with one or combination of more than 2 of magnesium nitrate, copper nitrate, ferric nitrate, zinc nitrate, magnesium sulfate, ferrous sulfate, aluminum sulfate and potassium nitrate, then forming with binder and peptizer to prepare the catalyst, which is used for synthesizing 6-aminocapronitrile by reaction of caprolactam and ammonia gas.
Chinese patent CN107739318A (a method and a device for preparing 6-aminocapronitrile by a caprolactam liquid phase method) provides a liquid phase process method for preparing 6-aminocapronitrile by taking caprolactam and ammonia gas as raw materials in 2 steps, wherein the reaction temperature is 300-500 ℃, and the catalyst is phosphoric acid or phosphate.
The catalyst used in Chinese patent (a device and a method for preparing 6-aminocapronitrile in gas phase) is to load phosphoric acid or phosphate onto an alumina or silica carrier, wherein the active component accounts for 0.1-10% of the mass of the carrier, comprises any one or at least 2 combinations of phosphoric acid, polyphosphoric acid, magnesium phosphate, aluminum phosphate, calcium sulfate and boron phosphate, and is used for preparing 6-aminocapronitrile by ammoniation and dehydration of caprolactam in a fluidized bed.
Chinese patent CN113087641A proposes a 2-step process for preparing 6-aminocapronitrile from cyclohexanone oxime, i.e. cyclohexanone oxime is rearranged into caprolactam by zeolite molecular sieve, and then aminated into 6-aminocapronitrile by a catalyst using alumina and/or silica as carrier and phosphoric acid and/or phosphate as active component.
In these methods, the catalysts have problems of low activity, low efficiency, large pollution, many byproducts, and the like.
Disclosure of Invention
The invention aims to provide a catalyst for preparing 6-aminocapronitrile, which has good low-temperature activity catalysis, can be used for synthesizing 6-aminocapronitrile at a temperature of 250-500 ℃, can obtain better yield and has no environmental pollution.
The technical scheme adopted by the invention is as follows: a catalyst for synthesizing 6-aminocapronitrile from cyclohexanone oxime or caprolactam in one step uses a P-containing molecular sieve as an active component, wherein the active component of the P-containing molecular sieve accounts for 10% -80% by dry weight, and the balance is a carrier and a binder, and the catalyst is in the shape of microspheres of 1 micron-300 microns or particles of 0.5 mm-10 mm.
Another object of the present invention is to provide a method for preparing the catalyst for synthesizing 6-aminocapronitrile from cyclohexanone oxime or caprolactam in one step, which comprises the following steps:
(1) mixing molecular sieve and phosphorus-containing compound solution uniformly to obtain thick slurry, in which the dry weight of molecular sieve and P in phosphorus-containing compound are mixed2O5The mass ratio is 1: 0.001-0.08, the slurry is directly dried at 100-300 ℃ and roasted at 350-600 ℃ to form solid powder, and the P-containing molecular sieve is prepared;
(2) mixing the P-containing molecular sieve with a carrier and deionized water, adding a binder, continuously mixing or uniformly rolling, performing spray forming or extrusion molding, and then drying and roasting to prepare the catalyst, wherein the P-containing molecular sieve accounts for 10-80% of the dry basis of the carrier and the deionized water.
The invention can also adopt the following preparation method for synthesizing the catalyst of 6-aminocapronitrile from cyclohexanone oxime or caprolactam by one step, firstly mixing and molding the molecular sieve, the carrier and the binder, then dipping the molecular sieve with the phosphorus-containing compound according to the dry basis proportion, and drying and roasting the mixture to prepare the catalyst, wherein the preparation process comprises the following steps:
(1) mixing the molecular sieve with a carrier and deionized water, adding a binder, wherein the molecular sieve accounts for 10-80% of the dry basis, continuously mixing or uniformly rolling, performing spray forming or extrusion molding, and then drying and roasting to prepare the catalyst.
(2) And (2) mixing and soaking the catalyst prepared in the step (1) with a phosphorus compound-containing solution uniformly, wherein the mass ratio of the dry weight of a molecular sieve in the catalyst to the mass of P2O5 in the phosphorus compound is 1: 0.001-0.08, and the slurry is directly dried at 100-300 ℃ and roasted at 350-600 ℃ to obtain the final catalyst.
The molecular sieve refers to ZSM-5, mordenite, a pure silicon MFI structure molecular sieve, Beta, ZSM-11, HY/USY, EU-1, SAPO molecular sieve and MCM-41 molecular sieve.
The carrier is silica gel, white carbon black, titanium dioxide, zirconium hydroxide-zirconia powder, pseudo-boehmite, activated clay, kaolin, halloysite and diatomite.
The binder is one or a mixture of more of silica sol, alumina sol, aluminum phosphate gel, silica-alumina gel and acidified pseudo-boehmite gel.
The phosphorus-containing compound refers to phosphoric acid, phosphorous acid, ammonium phosphate, ammonium phosphite, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
The catalyst has simple preparation process, is used for synthesizing 6-aminocapronitrile from cyclohexanone oxime or caprolactam serving as a raw material, the synthesis reaction is carried out at the temperature of 250-500 ℃, the conversion rate of the cyclohexanone oxime or caprolactam can reach 99.0 percent, the selectivity of the 6-aminocapronitrile reaches more than 95 percent, and the catalyst has the advantages of high conversion rate, high yield and few byproducts.
Detailed Description
The process of the invention is further illustrated by the following specific examples.
The raw materials adopted by the embodiments of the invention are specifically as follows:
ZSM-5 molecular sieve, H type, Si/Al ratio of 50, 100, Yueyang gathering chemical industry Co.
8.3 percent of silica gel by burning, and Qingdao sea products.
Pseudo-boehmite, alumina content 68%, a product of Shandong aluminum industry Co.
Silica sol, 30% content, product of Yueyang Heng faith New Material company
Kaolin, a product of suzhou kaolin corporation.
Example 1
This example is the preparation of 2P-modified molecular sieves.
Taking the ratio of silicon to aluminum (SiO)2/Al2O3) 1200g (2.1% burn) of 100 ZSM-5 molecular sieve was added to 1000g of deionized water containing 33g of ammonium dihydrogen phosphate, mixed for 30min, and then dried at 120 ℃ for 6h and calcined at 500 ℃ for 3h to give a modified molecular sieve P01, which was analyzed to have a burn of 3.2% and a P2O5 content of 1.6% after cooling.
Taking the ratio of silicon to aluminum (SiO)2/Al2O3) 2000g of 50 ZSM-5 molecular sieve (ignition 2.1%) was added to 1800g of deionized water containing 126g of ammonium dihydrogen phosphate, mixed for 45min, dried at 120 ℃ for 6h and calcined at 500 ℃ for 3h to give a modified molecular sieve P02, which was analyzed to have an ignition of 3.0% and a P2O5 content of 3.6% after cooling.
Example 2
Taking 110g of modified molecular sieve P01, adding 130g of silica gel, 110g of pseudo-boehmite and 550g of deionized water, mixing and pulping uniformly, grinding by a colloid mill, adding 160g of 65% nitric acid, continuously mixing for 2h, spray-drying and molding the materials, drying for 4h at 200 ℃, and roasting for 2h at 550 ℃ to obtain the catalyst cat-1.
Example 3
Taking 110g of modified molecular sieve P01, adding 65g of silica gel, 85g of kaolin, 110g of pseudo-boehmite and 500g of deionized water, mixing and pulping uniformly, grinding by a colloid mill, adding 160g of 65% nitric acid, continuously mixing for 2h, spray-drying and molding the materials, drying for 4h at 200 ℃, and roasting for 3h at 550 ℃ to obtain the catalyst cat-2.
Example 4
Taking 180g of modified molecular sieve P01, adding 192g of silica gel and 560g of deionized water, mixing and pulping uniformly, and grinding by a colloid mill to obtain molecular sieve slurry for later use.
Taking 110g of pseudo-boehmite and 220g of deionized water, mixing, adding 45g of 75% phosphoric acid and 260g of 65% nitric acid, uniformly mixing, heating to 80 ℃, and reacting for 2h to obtain the alumina gel.
Adding aluminium glue into the molecular sieve thick liquid, continuing to mix 2h, the material carries out spray drying shaping to at 200 ℃ dry 6h, 550 ℃ calcination 3h, obtain catalyst cat-3.
Example 5
258g of modified molecular sieve P01 is taken, 110g of silica gel and 550g of deionized water are added, and the mixture is uniformly mixed and pulped and is finely ground by a colloid mill to obtain molecular sieve slurry for later use.
183g of pseudo-boehmite and 250g of deionized water are mixed, 45g of 75% phosphoric acid and 280g of 65% nitric acid are added, the mixture is uniformly mixed, the temperature is raised to 90 ℃, and the reaction lasts for 2 hours, so that the alumina gel is obtained.
Adding aluminium glue into the molecular sieve thick liquid, continuing to mix 2h, the material carries out spray drying shaping to at 200 ℃ dry 6h, 550 ℃ calcination 2h, obtain catalyst cat-4.
Example 6
500g of modified molecular sieve P02, 12g of sesbania powder, 10g of methylcellulose and 220g of pseudo-boehmite are uniformly mixed, then 0.6% of phosphoric acid and 3% of dilute nitric acid mixed solution 120g are slowly sprayed and added, after uniform mixing and kneading, 2mm clover strips are extruded, then the mixture is dried at 120 ℃ for 12h, and then the mixture is roasted at 500 ℃ for 4h to obtain the bar-shaped catalyst cat-5.
Example 7
230g of modified molecular sieve P01 is taken, 236g of kaolin and 900g of deionized water are added, the mixture is uniformly mixed and pulped and is milled by a colloid mill, 366g of 30% silica sol is added, the mixture is continuously mixed for 2 hours, the material is subjected to spray drying and molding, and is dried for 6 hours at 200 ℃ and roasted for 3 hours at 550 ℃, and the catalyst cat-6 is obtained.
Example 8
258g of modified molecular sieve P02 is taken, 110g of silica gel and 550g of deionized water are added, and the mixture is uniformly mixed and pulped and is finely ground by a colloid mill to obtain molecular sieve slurry for later use.
183g of pseudo-boehmite and 250g of deionized water are mixed, 45g of 75% phosphoric acid and 280g of 65% nitric acid are added, the mixture is uniformly mixed, the temperature is raised to 90 ℃, and the reaction lasts for 2 hours, so that the alumina gel is obtained.
Adding aluminium glue into the molecular sieve thick liquid, continuing to mix 2h, the material carries out spray drying shaping to at 200 ℃ dry 6h, 550 ℃ calcination 2h, obtain catalyst cat-7.
Example 9
Taking 180g of modified molecular sieve P02, adding 192g of silica gel and 560g of deionized water, mixing and pulping uniformly, and grinding by a colloid mill to obtain molecular sieve slurry for later use.
And (2) mixing 110g of pseudo-boehmite and 220g of deionized water, adding 48g of 75% phosphoric acid and 250g of 65% nitric acid, uniformly mixing, heating to 85 ℃, and reacting for 2h to obtain the alumina gel.
Adding aluminium glue into the molecular sieve thick liquid, continuing to mix 2h, the material carries out spray drying shaping to at 200 ℃ dry 6h, 550 ℃ calcination 3h, obtain catalyst cat-8.
Example 10
This example is an evaluation of the catalyst.
The catalyst was evaluated by a fixed bed evaluation apparatus, the catalyst loading was 80g, the upper and lower sides were isolated by asbestos gauze and quartz sand packing, the raw materials were ethanol solution containing 60% cyclohexanone oxime and ammonia gas, the space velocity was 1.2h-1The cyclohexanone oxime/ethanol solution is mixed with ammonia and subjected to rearrangement and ammonolysis reaction at a temperature of 320 ℃ on a bed layer, the molar ratio of ammonia gas to cyclohexanone oxime is 10, the reaction pressure is 0.2Mpa, and the cyclohexanone oxime is aminated and dehydrated to synthesize the 6-amino-caprone.
Cooling the ammonolysis solution, then feeding the cooled ammonolysis solution into a gas-liquid separation tank, collecting a liquid product, measuring the content of each component in the liquid product by adopting a gas chromatography area normalization method, calculating the conversion rate of cyclohexanone oxime according to the content of cyclohexanone oxime in the liquid product, and calculating the total selectivity of caprolactam and 6-aminocapronitrile in the liquid product according to the content of caprolactam and 6-aminocapronitrile in the liquid product, wherein the calculation formula is as follows:
cyclohexanone oxime conversion% = 1-cyclohexanone oxime content in liquid sample/cyclohexanone oxime content in raw material liquid;
caprolactam selectivity% = caprolactam content in liquid sample%/cyclohexanone oxime content in feed liquid;
selectivity% of 6-aminocapronitrile = 6-aminocapronitrile content in liquid sample%/cyclohexanone oxime content in raw material liquid;
Figure 321057DEST_PATH_IMAGE001
the evaluation results are shown in Table 1.
The activity and the selectivity of the catalyst are improved by the proper P modified molecular sieve, the conversion rate of the cyclohexanone oxime can be improved to more than 99% by the preferable catalyst, and the selectivity of the target product 6-aminocapronitrile can also be up to more than 96%.
Example 11
This example also evaluates the catalyst.
The catalyst was evaluated by a fixed bed evaluation apparatus, the catalyst loading was 80g, the upper and lower sides were isolated by asbestos gauze and quartz sand packing, the raw materials were ethanol solution containing 60% caprolactam and ammonia gas, the space velocity was 1.2h-1The cyclohexanone oxime/ethanol solution is mixed with ammonia and subjected to rearrangement and aminolysis reaction by a bed layer at 320 ℃, the molar ratio of ammonia gas to cyclohexanone oxime is 4, the reaction pressure is 0.50Mpa, and the 6-aminocapronitrile is synthesized.
Cooling the ammonolysis solution, then feeding the cooled ammonolysis solution into a gas-liquid separation tank, collecting a liquid product, measuring the content of each component in the liquid product by adopting a gas chromatography area normalization method, calculating the conversion rate of caprolactam according to the content of caprolactam in the liquid product, and calculating the selectivity according to the content of 6-aminocapronitrile in the liquid product, wherein the calculation formula is as follows:
caprolactam conversion% = 1-caprolactam content in liquid sample/caprolactam content in raw material liquid;
selectivity% of 6-aminocapronitrile = 6-aminocapronitrile content% in liquid sample/caprolactam content% in raw material liquid;
catalyst sample numbering Caprolactam conversion% 6-aminocapronitrile Selectivity%
cat-1 99.10% 93.50%
cat-2 99.20% 92.60%
cat-3 99.60% 98.60%
cat-4 99.80% 98.80%
cat-5 99.80% 99.10%
cat-6 99.60% 99.50%
cat-7 99.80% 99.60%
cat-8 99.50% 98.90%
The evaluation results are shown in Table 2.
The activity and the selectivity of the catalyst are improved by the proper P modified molecular sieve, the conversion rate of caprolactam can be improved to more than 99% by the preferable catalyst, and the selectivity of the target product 6-aminocapronitrile can also reach more than 99%.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may be modified or some technical features may be equivalently replaced, and the modifications or the replacements do not cause the essence of the corresponding technical solutions to depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and the equivalents of the raw materials of the product of the present invention, the addition of the auxiliary components, the selection of the specific modes, and the like all fall within the protection scope and the disclosure scope of the present invention.

Claims (8)

1. A catalyst for synthesizing 6-aminocapronitrile from cyclohexanone oxime or caprolactam in one step is characterized in that: the catalyst uses a P-containing molecular sieve as an active component, wherein the active component contains 10-80% of the P-containing molecular sieve, 0-50% of a carrier, 10-50% of a binder, and the catalyst is microspheres with the shape of 1-300 microns or particles with the shape of 0.5-10 mm.
2. The process according to claim 1, wherein the process comprises the steps of:
(1) mixing molecular sieve and phosphorus-containing compound solution uniformly to obtain thick slurry, in which the dry weight of molecular sieve and P in phosphorus-containing compound are mixed2O5The mass ratio is 1: 0.001-0.08, the slurry is directly dried at 100-300 ℃ and roasted at 350-600 ℃ to formSolid powder to prepare a molecular sieve containing P;
(2) mixing the P-containing molecular sieve with a carrier and deionized water, adding a binder, continuously mixing or uniformly rolling, performing spray forming or extrusion molding, and then drying and roasting to prepare the catalyst, wherein the P-containing molecular sieve accounts for 10-80% of the dry basis of the carrier and the deionized water.
3. The method according to claim 1, wherein the molecular sieve, the carrier and the binder are mixed and molded, then the catalyst is impregnated with the phosphorus-containing compound according to the dry basis ratio, and the catalyst is prepared after drying and roasting, and the preparation process comprises the following steps:
(1) mixing a molecular sieve with a carrier and deionized water, adding a binder, continuously mixing or uniformly rolling, performing spray forming or extrusion molding, and then drying and roasting to prepare a catalyst, wherein the molecular sieve accounts for 10-80% in terms of dry basis;
(2) mixing and soaking the catalyst prepared in the step (1) with a phosphorus compound-containing solution uniformly, wherein the weight of the molecular sieve in the catalyst is equal to that of P in the phosphorus compound2O5The mass ratio is 1: 0.001-0.08, the slurry is directly dried at 100-300 ℃ and roasted at 350-600 ℃ to obtain the final catalyst.
4. The method for preparing the catalyst for one-step synthesis of 6-aminocapronitrile from cyclohexanone oxime or caprolactam according to claim 2 or 3, wherein the molecular sieve is ZSM-5, mordenite, pure silicon MFI structure molecular sieve, Beta, ZSM-11, HY/USY, EU-1, SAPO molecular sieve or MCM-41 molecular sieve.
5. The method for preparing the catalyst for one-step synthesis of 6-aminocapronitrile from cyclohexanone oxime or caprolactam according to claim 2 or 3, wherein the carrier is silica gel, white carbon black, titanium dioxide, zirconium hydroxide-zirconia powder, pseudoboehmite, activated clay, kaolin, halloysite or diatomite.
6. The method for preparing the catalyst for one-step synthesis of 6-aminocapronitrile from cyclohexanone oxime or caprolactam according to claim 2 or 3, wherein the binder is one or more of silica sol, alumina phosphate gel, silica alumina gel and acidified pseudoboehmite gel.
7. The method according to claim 2 or 3, wherein the phosphorus-containing compound is phosphoric acid, phosphorous acid, ammonium phosphate, ammonium phosphite, diammonium hydrogen phosphate, or ammonium dihydrogen phosphate.
8. The preparation method of the catalyst for one-step synthesis of 6-aminocapronitrile from cyclohexanone oxime or caprolactam according to claims 1 to 7, wherein the prepared catalyst is used in a process for synthesizing 6-aminocapronitrile by reacting cyclohexanone oxime or caprolactam with ammonia gas.
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CN114768865A (en) * 2022-05-24 2022-07-22 陈天然 Catalyst for preparing 6-aminocapronitrile from cyclohexanone oxime and application thereof
CN114832851A (en) * 2022-05-25 2022-08-02 北京旭阳科技有限公司 Fixed bed catalyst for preparing 6-aminocapronitrile by ammoniation of caprolactam and preparation method and application thereof
CN114917952A (en) * 2022-06-30 2022-08-19 中国天辰工程有限公司 Preparation method of intermediate catalyst for preparing hexamethylene diamine from caprolactam
CN116393163A (en) * 2023-03-27 2023-07-07 湖北兴发化工集团股份有限公司 Combined catalyst for synthesizing 6-aminocapronitrile by cyclohexanone oxime one-step method and preparation method thereof

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