CN117299198A - Catalyst for preparing 6-aminocapronitrile by ammonolysis of caprolactam, preparation method and application - Google Patents
Catalyst for preparing 6-aminocapronitrile by ammonolysis of caprolactam, preparation method and application Download PDFInfo
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- CN117299198A CN117299198A CN202211737377.6A CN202211737377A CN117299198A CN 117299198 A CN117299198 A CN 117299198A CN 202211737377 A CN202211737377 A CN 202211737377A CN 117299198 A CN117299198 A CN 117299198A
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- catalyst
- caprolactam
- aminocapronitrile
- molecular sieve
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005915 ammonolysis reaction Methods 0.000 title claims abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 241000269350 Anura Species 0.000 claims abstract description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000002940 palladium Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 36
- 239000011259 mixed solution Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 10
- 238000011049 filling Methods 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000001493 electron microscopy Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- -1 alkaline earth metal salt Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing 6-aminocapronitrile by ammonolysis of caprolactam, a preparation method and application thereof, wherein the catalyst is a palladium-loaded SAPO molecular sieve. For the reaction of preparing 6-aminocapronitrile by ammonolysis of caprolactam, the catalyst has the advantages of low reaction temperature, high caprolactam conversion rate, high target product selectivity, high catalyst recycling performance, simple catalyst preparation method and the like, and has good industrialized prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of 6-aminocapronitrile, and particularly relates to a SAPO molecular sieve supported palladium catalyst for preparing 6-aminocapronitrile by ammonolysis of caprolactam, and a preparation method and application thereof.
Background
6-aminocapronitrile is an important chemical intermediate, an important raw material for hexamethylenediamine, used in large quantities to produce nylon 66 and nylon 610.
The production process of hexamethylenediamine mainly comprises a butadiene method, an acrylonitrile method, an adipic acid method and the like, wherein the butadiene method is a process for producing hexamethylenediamine on a large scale, however, a great amount of industrial three wastes can be generated due to the use of highly toxic chemicals, and the post-treatment cost is high; the acrylonitrile method has high energy consumption, and byproducts generated in the reaction can cause high subsequent separation cost; the adipic acid method has the defects of multiple process steps, high raw material cost and low product selectivity, and the process is basically eliminated.
The caprolactam method is to take caprolactam as a raw material, produce 6-aminocapronitrile after ammoniation and dehydration, and then hydrogenate to produce hexamethylenediamine. The caprolactam method has the advantages of simple reaction steps, environment-friendly process, sufficient raw material supply and high product selectivity; as caprolactam continues to expand, the excess capacity can lead to a decrease in the price of caprolactam, and the process for preparing hexamethylenediamine using caprolactam as a raw material gradually exhibits a competitive advantage.
At present, one or more of phosphate, alkaline earth metal oxide, transition metal oxide, silicon dioxide and aluminum oxide are used as catalysts for preparing 6-aminocapronitrile from caprolactam, but the catalysts have low reaction activity, the reaction temperature is 300-650 ℃, and the energy consumption is serious. For example, patent CN110404582a reports a method for preparing 6-aminocapronitrile by catalyzing caprolactam with a phosphorus-aluminum molecular sieve as a catalyst, wherein the reaction is carried out at 420-500 ℃; patent CN214735474U reports a method for preparing 6-aminocapronitrile by catalyzing caprolactam by using phosphoric acid/phosphate as a catalyst, wherein the reaction is carried out at 300-500 ℃; patent CN202010999422.X reports a method for preparing 6-aminocapronitrile by catalyzing caprolactam with alkaline earth metal oxide as a catalyst, wherein the reaction is carried out at 300-650 ℃; patent CN201911388128.9 reports a method for preparing 6-aminocapronitrile by catalyzing caprolactam by using alkaline earth metal salt/transition metal salt as a catalyst, wherein the reaction is carried out at 330-430 ℃; patent CN202110882617.0 reports a method for preparing 6-aminocapronitrile by catalyzing caprolactam by using a silicon-aluminum-phosphorus molecular sieve as a catalyst, wherein the reaction is carried out at 300-500 ℃.
Disclosure of Invention
In order to solve the problems of low activity and high energy consumption caused by overhigh reaction temperature of the existing catalyst, the invention provides a catalyst capable of preparing 6-aminocapronitrile by ammonolysis of caprolactam at a lower temperature and a preparation method thereof. The catalyst prepared by the method is simple in preparation method, the catalytic activity is obviously improved after a small amount of palladium is loaded, the temperature required by the reaction can be reduced, the catalyst has excellent catalytic activity at 200-300 ℃, and the selectivity of 6-aminocapronitrile converted from Pd per mole per unit time is higher than 99.5 percent (TOF) 55.3,6-aminocapronitrile.
The invention is realized by the following technical scheme:
a catalyst for preparing 6-aminocapronitrile by ammonolysis of caprolactam is prepared by adopting a palladium-loaded SAPO molecular sieve.
Preferably, the palladium loading is 0.1-1% of the mass fraction of the SAPO molecular sieve.
Preferably, the SAPO molecular sieve is one or more of SAPO-5, SAPO-11 or SAPO-34.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) Immersing a SAPO molecular sieve in a solvent containing palladium salt, carrying out ultrasonic impregnation, and then drying to obtain a precursor;
(2) And roasting the precursor at 400-700 ℃ in an air atmosphere to obtain the precursor.
Preferably, the palladium salt in step (1) is palladium acetate.
Preferably, the solvent in the step (1) is one or more of toluene, acetonitrile, diethyl ether or acetone.
Preferably, the ultrasonic impregnation time in the step (1) is 12-48 hours.
Preferably, the drying temperature in the step (1) is 60-120 ℃.
Preferably, the roasting time in the step (2) is 4-10 hours.
The invention also provides application of the catalyst, which comprises the following steps:
and adding the catalyst into a reactor, introducing caprolactam and ammonia gas into the reactor, and reacting at 200-300 ℃ to obtain the 6-aminocapronitrile.
Preferably, the pressure of the reaction is 1MPa or less.
Preferably, the space velocity in the reactor is 0.5-5 h -1 。
Preferably, the molar ratio of caprolactam to ammonia is 1:5-50.
The invention has the beneficial effects that:
according to the catalyst disclosed by the invention, palladium is loaded on the SAPO molecular sieve, so that the activity of the catalyst in the reaction of preparing 6-aminocapronitrile from caprolactam is obviously improved, and satisfactory conversion rate and selectivity can be obtained at the temperature of 200-300 ℃, and compared with the existing high-temperature reaction method, the catalyst provided by the invention is beneficial to reducing the process energy consumption and avoiding carbon deposition of the catalyst.
Drawings
Fig. 1 is an XRD pattern of the catalyst prepared in example 1.
FIG. 2 is an electron microscopy morphology of the catalyst prepared in example 3.
FIG. 3 is an electron microscopy morphology of the catalyst prepared in example 3.
Fig. 4 is an XRD pattern of the catalyst prepared in example 3.
FIG. 5 is a BET plot of the catalyst prepared in example 8.
FIG. 6 is an electron microscopy morphology of the catalyst prepared in example 10.
FIG. 7 is an electron microscopy morphology of the catalyst prepared in example 10.
Detailed description of the preferred embodiments
Example 1
6g of SAPO-5 molecular sieve is weighed, 3.5g of acetonitrile and 0.0127g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 24 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into an oven at 80 ℃ for drying for 8 hours, and roasting the materials for 5 hours in an air atmosphere at 550 ℃ for molding.
Filling 4g of the prepared catalyst into a fixed bed, wherein the reaction temperature is 200 ℃, the feeding mole ratio of ammonia gas to caprolactam is 20:1, and the space velocity is 3h -1 TOF (moles of Pd converted to 6-aminocapronitrile per unit time) was 0.88 and selectivity to 6-aminocapronitrile product was greater than 99.5%.
Example 2
6g of SAPO-11 molecular sieve is weighed, 3.5g of acetonitrile and 0.0127g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 36 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into an oven at 80 ℃ for drying for 8 hours, and roasting the materials for 10 hours in an air atmosphere at 400 ℃ for molding.
Filling 4g of the prepared catalyst into a fixed bed, wherein the reaction temperature is 200 ℃, the feeding mole ratio of ammonia gas to caprolactam is 50:1, and the space velocity is 3h -1 TOF was 2.8 and the selectivity of the product 6-aminocapronitrile was greater than 99.5%.
Example 3
6g of SAPO-34 molecular sieve is weighed, 3.5g of toluene and 0.0254g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 24 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into a 60 ℃ oven for drying for 8 hours, and roasting the materials for 5 hours in an air atmosphere at 550 ℃ for molding.
Filling 4g of the prepared catalyst into a fixed bed, wherein the reaction temperature is 250 ℃, the feeding mole ratio of ammonia gas to caprolactam is 20:1, and the space velocity is 3h -1 TOF was 16.9 and the selectivity of the product 6-aminocapronitrile was greater than 99.5%.
Example 4
12g of SAPO molecular sieve is weighed, 7g of acetonitrile and 0.0508g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is subjected to ultrasonic impregnation for 24 hours in a sealed environment. And then washing and filtering the materials, putting the materials into a 100 ℃ oven for drying for 8 hours, and roasting the materials for 7 hours in an air atmosphere at 450 ℃ for molding.
10g of the catalyst prepared was packed in a fixed bed at a reaction temperature of 250℃and a molar ratio of ammonia to caprolactam of 20:1 and a space velocity of 0.5h -1 TOF was 31.0 and selectivity to product 6-aminocapronitrile was greater than 99.5%.
Example 5
6g of SAPO molecular sieve is weighed, 3.5g of acetonitrile and 0.0635g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 12 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into an oven at 80 ℃ for drying for 8 hours, and roasting the materials for 6 hours in an air atmosphere at 500 ℃ for molding.
Filling 4g of the prepared catalyst into a fixed bed, wherein the reaction temperature is 250 ℃, the feeding mole ratio of ammonia gas to caprolactam is 10:1, and the space velocity is 3h -1 TOF was 36.9 and the selectivity of the product 6-aminocapronitrile was greater than 99.5%.
Example 6
6g of SAPO molecular sieve is weighed, 3.5g of acetonitrile and 0.0635g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 24 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into an oven at 80 ℃ for drying for 8 hours, and roasting the materials for 5 hours in an air atmosphere at 600 ℃ for molding.
Filling 4g of the prepared catalyst into a fixed bed, wherein the reaction temperature is 250 ℃, the feeding mole ratio of ammonia gas to caprolactam is 20:1, and the space velocity is 3h -1 TOF was 47.4 and the selectivity of the product 6-aminocapronitrile was greater than 99.5%.
Example 7
6g of SAPO molecular sieve is weighed, 3.5g of acetonitrile and 0.0635g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 24 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into a baking oven at 120 ℃ for drying for 8 hours, and roasting the materials for 4 hours in an air atmosphere at 700 ℃ for molding.
4g of the catalyst thus obtained was packed in a fixed bedIn the reaction, the reaction temperature is 250 ℃, the feeding mole ratio of ammonia gas and caprolactam is 5:1, and the airspeed is 3h -1 TOF was 25.9 and the selectivity of the product 6-aminocapronitrile was greater than 99.5%.
Example 8
12g of SAPO molecular sieve is weighed, 7g of diethyl ether and 0.127g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 24 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into an oven at 80 ℃ for drying for 8 hours, and roasting the materials for 5 hours in an air atmosphere at 550 ℃ for molding.
8g of the catalyst prepared was packed in a fixed bed at a reaction temperature of 280℃and a molar ratio of ammonia to caprolactam of 40:1 and a space velocity of 1.5h -1 TOF was 55.3 and the selectivity of the product 6-aminocapronitrile was greater than 99.5%.
Example 9
12g of SAPO molecular sieve is weighed, 7g of acetonitrile and 0.127g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 48 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into an oven at 80 ℃ for drying for 8 hours, and roasting the materials for 5 hours in an air atmosphere at 650 ℃ for molding.
8g of the catalyst prepared was packed in a fixed bed at a reaction temperature of 280℃and a molar ratio of ammonia to caprolactam of 40:1 and a space velocity of 1.5h -1 TOF was 52.8 and selectivity to product 6-aminocapronitrile was greater than 99.5%.
Example 10
6g of SAPO molecular sieve is weighed, 3.5g of acetonitrile and 0.127g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 24 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into a 60 ℃ oven for drying for 8 hours, and roasting the materials for 5 hours in an air atmosphere at 550 ℃ for molding.
2.4g of the catalyst prepared was filled into a fixed bed, the reaction temperature was 300℃and the molar ratio of ammonia to caprolactam fed was 20:1, the space velocity was 5h -1 TOF was 26.8 and the selectivity of the product 6-aminocapronitrile was greater than 99.5%.
Example 11
6g of SAPO molecular sieve is weighed, 5g of acetone and 0.127g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is subjected to ultrasonic impregnation for 24 hours in a sealed environment. And then washing and filtering the materials, putting the materials into an oven at 80 ℃ for drying for 8 hours, and roasting the materials for 5 hours in an air atmosphere at 550 ℃ for molding.
Filling 4g of the prepared catalyst into a fixed bed, wherein the reaction temperature is 300 ℃, the feeding mole ratio of ammonia gas to caprolactam is 5:1, and the space velocity is 3h -1 TOF was 19.1 and the selectivity of the product 6-aminocapronitrile was greater than 99.5%.
Example 12
6g of SAPO molecular sieve is weighed, 3.5g of acetonitrile and 0.127g of palladium acetate are weighed to prepare a mixed solution, the mixed solution is added into the SAPO molecular sieve, and the mixed solution is immersed for 24 hours in an ultrasonic manner under a sealed environment. And then washing and filtering the materials, putting the materials into an oven at 80 ℃ for drying for 8 hours, and roasting the materials for 5 hours in an air atmosphere at 550 ℃ for molding.
Filling 4g of the prepared catalyst into a fixed bed, wherein the reaction temperature is 300 ℃, the feeding mole ratio of ammonia gas to caprolactam is 20:1, and the space velocity is 3h -1 TOF was 29.3 and the selectivity of the product 6-aminocapronitrile was greater than 99.5%.
Claims (10)
1. A catalyst for preparing 6-aminocapronitrile by ammonolysis of caprolactam is characterized in that the catalyst is a palladium-loaded SAPO molecular sieve.
2. The catalyst of claim 1, wherein the palladium loading is 0.1-1% by mass of the SAPO molecular sieve.
3. The catalyst of claim 1, wherein the SAPO molecular sieve is one or more of SAPO-5, SAPO-11 or SAPO-34.
4. A process for the preparation of a catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
(1) Immersing a SAPO molecular sieve in a solvent containing palladium salt, carrying out ultrasonic impregnation, and then drying to obtain a precursor;
(2) And roasting the precursor at 400-700 ℃ in an air atmosphere to obtain the precursor.
5. The method according to claim 4, wherein the palladium salt in the step (1) is palladium acetate.
6. The method according to claim 4, wherein the solvent in the step (1) is one or more of toluene, acetonitrile, diethyl ether or acetone.
7. The method according to claim 4, wherein the ultrasonic impregnation time in the step (1) is 12 to 48 hours.
8. The method according to claim 4, wherein the drying temperature in the step (1) is 60 to 120 ℃.
9. The method according to claim 4, wherein the baking time in the step (2) is 4 to 10 hours.
10. Use of a catalyst according to any one of claims 1 to 3, comprising:
and adding the catalyst into a reactor, introducing caprolactam and ammonia gas into the reactor, and reacting at 200-300 ℃ to obtain the 6-aminocapronitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211737377.6A CN117299198A (en) | 2022-12-31 | 2022-12-31 | Catalyst for preparing 6-aminocapronitrile by ammonolysis of caprolactam, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211737377.6A CN117299198A (en) | 2022-12-31 | 2022-12-31 | Catalyst for preparing 6-aminocapronitrile by ammonolysis of caprolactam, preparation method and application |
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| Publication Number | Publication Date |
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| CN117299198A true CN117299198A (en) | 2023-12-29 |
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| CN202211737377.6A Pending CN117299198A (en) | 2022-12-31 | 2022-12-31 | Catalyst for preparing 6-aminocapronitrile by ammonolysis of caprolactam, preparation method and application |
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| Country | Link |
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- 2022-12-31 CN CN202211737377.6A patent/CN117299198A/en active Pending
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