CN117160522A - Catalyst for preparing cyclohexanol by cyclohexene hydration, and preparation method and application thereof - Google Patents
Catalyst for preparing cyclohexanol by cyclohexene hydration, and preparation method and application thereof Download PDFInfo
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 30
- 230000036571 hydration Effects 0.000 title claims abstract description 27
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 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 73
- 239000002808 molecular sieve Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000010306 acid treatment Methods 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 sulfuric acid Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysis, and discloses a catalyst for preparing cyclohexanol by cyclohexene hydration and a preparation method thereof, wherein the catalyst comprises the following steps: adding ZSM-5 molecular sieve into alkali solution for desilication reaction; step two, the ZSM-5 molecular sieve treated in the step one is sequentially subjected to filtration, centrifugal separation, washing and drying treatment to obtain a pretreated molecular sieve; and thirdly, adding the pretreated molecular sieve into a metal salt solution for ion exchange, and then sequentially filtering, centrifugally separating, washing, drying, acid treatment, filtering or centrifugally separating, washing, drying and roasting to obtain the metal modified ZSM-5 molecular sieve catalyst. Adding ZSM-5 molecular sieve into alkali solution for desilication reaction, separating, washing and drying to obtain pretreated molecular sieve, adding pretreated molecular sieve into metal salt solution for ion exchange, separating, washing, drying, acid treatment and roasting to obtain the modified ZSM-5 molecular sieve catalyst.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a catalyst for preparing cyclohexanol by cyclohexene hydration, a preparation method and application thereof.
Background
The new nylon material is used as an important base stone in modern industry and high and new technology, and is widely applied to chemical fiber, engineering plastic and other industries. Cyclohexanol is a key intermediate for producing nylon 66 and nylon 6, and is mainly used for producing adipic acid, caprolactam and the like, and the demand amount is increased year by year. The prior cyclohexanol production process mainly comprises three processes of a phenol hydrogenation process, a cyclohexane oxidation process and a cyclohexene hydration process, wherein the cyclohexene hydration process gradually becomes the main process for cyclohexanol production due to the advantages of high safety, high selectivity, low hydrogen consumption and the like.
Cyclohexene hydration reactions are typically acid catalyzed, early catalysts being mineral acids such as sulfuric acid, and have evolved into heterogeneous solid catalysts such as ZSM-5 molecular sieves. The traditional ZSM-5 molecular sieve is limited by the micropore aperture, the utilization efficiency of active sites in pore channels and the mass transfer diffusion rate are low, the cyclohexene reaction rate is low, the single pass conversion rate is low (generally lower than 10% in industry), and the traditional ZSM-5 molecular sieve becomes a key technical problem of industry commonality. In order to reduce the adverse effect of the molecular sieve micropore diffusion resistance on the mass transfer process, improve the utilization efficiency of the catalyst and further directionally regulate and control the catalytic activity, attempts are made to introduce mesopores or macropores into the microporous molecular sieve. The composite material with different scales and multi-stage pore canal structures not only has strong acidity, good hydrothermal stability and excellent shape selectivity of the microporous molecular sieve, but also has excellent mass transfer diffusion performance of mesoporous/macroporous pore canals, and becomes a hot spot and a front edge of research in the field of the current molecular sieve. ZL 112978750B discloses a post-treatment method for modifying a molecular sieve, which comprises the steps of firstly soaking the molecular sieve with organic alkali to obtain a pretreated molecular sieve, and then soaking the molecular sieve with high micropore structure retention, high acid site retention and micro-mesoporous structure composite molecular sieve with inorganic alkali, wherein the method does not relate to a ZSM-5 molecular sieve.
The existing industrial ZSM-5 molecular sieve catalyst has the problem of low activity, and the molecular sieve is required to be subjected to metal modification to make up for the defect in the aspect and improve the single-pass conversion rate in the reaction process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for preparing cyclohexanol by cyclohexene hydration, a preparation method and application thereof, and solves the problems of lower activity and lower single-pass conversion rate in the reaction process of the existing industrial ZSM-5 molecular sieve catalyst.
In order to achieve the above purpose, the invention is realized by the following technical scheme: a catalyst for preparing cyclohexanol by cyclohexene hydration and a preparation method thereof comprise the following steps:
adding ZSM-5 molecular sieve into alkali solution for desilication reaction;
step two, the ZSM-5 molecular sieve treated in the step one is sequentially subjected to filtration, centrifugal separation, washing and drying treatment to obtain a pretreated molecular sieve;
and thirdly, adding the pretreated molecular sieve into a metal salt solution for ion exchange, and then sequentially filtering, centrifugally separating, washing, drying, acid treatment, filtering or centrifugally separating, washing, drying and roasting to obtain the metal modified ZSM-5 molecular sieve catalyst.
Further preferably, in the first step, the alkali solution is an inorganic alkali or an organic alkali, wherein the inorganic alkali is one of sodium hydroxide, sodium carbonate, sodium bicarbonate or sodium metaaluminate, the organic alkali is tetrapropylammonium hydroxide, the concentration of the alkali solution is 0.1-1mol/L, and the mass ratio of the molecular sieve to the alkali solution is 1:5-20.
Further preferably, in the first step, the desilication reaction is carried out at a temperature of 40-80 ℃ for 0.5-6 hours.
Further preferably, in the second step, the washing and drying are respectively deionized water washing to be neutral, and drying is carried out for 1-12h at 100 ℃.
Further preferably, in the third step, the metal salt solution is one of potassium nitrate, magnesium nitrate, calcium nitrate or cerium nitrate, and the concentration is 0.01-0.1mol/L.
Further preferably, in the third step, the ion exchange treatment condition is that stirring is carried out for 0.5-4 hours at the temperature of 40-90 ℃, and the mass ratio of the molecular sieve to the metal salt solution is 1:2-20.
Further preferably, in the third step, the acid treatment is carried out in a hydrochloric acid solution of 0.5mol/L at 40-80℃for 3 hours.
Further preferably, in the third step, the baking is 2-8 hours at 400-600 ℃.
The catalyst for preparing cyclohexanol by cyclohexene hydration is used for cyclohexene hydration reaction to effectively raise the once-through conversion rate of cyclohexene.
The invention provides a catalyst for preparing cyclohexanol by cyclohexene hydration, a preparation method and application thereof. The beneficial effects are as follows:
the preparation method of the modified ZSM-5 molecular sieve catalyst is simple, and can effectively improve the once-through conversion rate of cyclohexene when being used for cyclohexene hydration reaction.
Drawings
FIG. 1 is an XRD spectrum of a molecular sieve and an unmodified molecular sieve obtained in examples 1 to 5 provided by the invention;
FIG. 2 is a SEM spectrum of a molecular sieve according to example 2 provided by the present invention;
FIG. 3 is a graph showing the N2 adsorption/desorption spectra of the molecular sieve obtained in example 3 provided by the present invention;
FIG. 4 is a NH3-TPD spectrum of the molecular sieve obtained in example 4 provided by the present invention;
FIG. 5 is a pyridine infrared spectrum of the molecular sieve obtained in example 5 provided by the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. 150mL of 0.4 mol/L sodium hydroxide solution is added into a three-neck flask, 15 g of ZSM-5 molecular sieve is weighed and added into the three-neck flask, the mixture is stirred for 1h at 50 ℃, the mixture is centrifuged and washed to be neutral by deionized water, and the mixture is dried in an oven at 100 ℃ for 12h to obtain the pretreated molecular sieve.
2. The pretreated molecular sieve was added to 150mL of 0.1 ml/L potassium nitrate solution, stirred at 80℃for 2h, then centrifuged and washed with deionized water to neutrality, and dried in an oven at 100℃for 12h.
3. The dried molecular sieve was added to 0.5mol/L hydrochloric acid solution, stirred at 80℃for 3 hours, then centrifuged and washed with deionized water to neutrality, and dried in an oven at 100℃for 12 hours. And roasting the dried sample in a muffle furnace at 550 ℃ for 5 hours to obtain the metal potassium modified ZSM-5 molecular sieve catalyst.
The catalyst prepared in this example was used in the direct hydration of cyclohexene: and (3) performing catalyst performance evaluation in a high-pressure reaction kettle, weighing 7.5g of catalyst, 100g of deionized water and 50g of cyclohexene, adding into the reaction kettle, sealing the reaction kettle, introducing nitrogen to replace air in the kettle, then introducing nitrogen again to 0.5MPa, starting mechanical stirring and heating, timing after the reaction kettle is heated to 120 ℃, rapidly cooling the reaction kettle to room temperature after 4 hours of reaction, separating and taking out an oil phase, and performing product analysis by using a gas chromatography (HP-1 capillary chromatographic column) with a hydrogen flame ionization detector (F ID).
Example two
1. 100mL of 0.8 mol/L sodium bicarbonate solution is added into a three-neck flask, 15 g of ZSM-5 molecular sieve is weighed and added into the three-neck flask, the mixture is stirred for 4 hours at 60 ℃, the mixture is centrifuged and washed to be neutral by deionized water, and the mixture is dried in an oven at 100 ℃ for 6 hours to obtain the pretreated molecular sieve.
2. The pretreated molecular sieve was added to 100mL of 0.05 mol/L magnesium nitrate solution, stirred for 2h at 60℃and then centrifuged and washed to neutrality with deionized water, and dried in an oven at 100℃for 6h.
3. The dried molecular sieve was added to 0.5mol/L hydrochloric acid solution, stirred at 60℃for 3 hours, then centrifuged and washed with deionized water to neutrality, and dried in an oven at 100℃for 6 hours. And roasting the dried sample in a muffle furnace at 500 ℃ for 4 hours to obtain the magnesium metal modified ZSM-5 molecular sieve catalyst.
The catalyst prepared in this example was used in the direct hydration of cyclohexene: and (3) performing catalyst performance evaluation in a high-pressure reaction kettle, weighing 7.5g of catalyst, 100g of deionized water and 50g of cyclohexene, adding into the reaction kettle, sealing the reaction kettle, introducing nitrogen to replace air in the kettle, then introducing nitrogen again to 0.5MPa, starting mechanical stirring and heating, timing after the reaction kettle is heated to 120 ℃, rapidly cooling the reaction kettle to room temperature after 4 hours of reaction, separating and taking out an oil phase, and performing product analysis by using a gas chromatography (HP-1 capillary chromatographic column) with a hydrogen flame ionization detector (F ID).
Example III
1. 200mL of 0.2 ml/L tetrapropylammonium hydroxide solution is added into a three-neck flask, 15 g of ZSM-5 molecular sieve is weighed and added into the three-neck flask, the mixture is stirred for 1h at 80 ℃, the mixture is centrifuged and washed to be neutral by deionized water, and the mixture is dried in an oven at 100 ℃ for 4h to obtain the pretreated molecular sieve.
2. The pretreated molecular sieve was added to 200mL of 0.01 mol/L cerium nitrate solution, stirred for 2h at 80℃and then centrifuged and washed to neutrality with deionized water, and dried in an oven at 100℃for 4h.
3. The dried molecular sieve was added to 0.5mol/L hydrochloric acid solution, stirred at 50℃for 3 hours, then centrifuged and washed with deionized water to neutrality, and dried in an oven at 100℃for 4 hours. And roasting the dried sample in a muffle furnace at 400 ℃ for 8 hours to obtain the cerium metal modified ZSM-5 molecular sieve catalyst.
The catalyst prepared in this example was used in the direct hydration of cyclohexene: and (3) performing catalyst performance evaluation in a high-pressure reaction kettle, weighing 7.5g of catalyst, 100g of deionized water and 50g of cyclohexene, adding into the reaction kettle, sealing the reaction kettle, introducing nitrogen to replace air in the kettle, then introducing nitrogen again to 0.5MPa, starting mechanical stirring and heating, timing after the reaction kettle is heated to 120 ℃, rapidly cooling the reaction kettle to room temperature after 4 hours of reaction, separating and taking out an oil phase, and performing product analysis by using a gas chromatography (HP-1 capillary chromatographic column) with a hydrogen flame ionization detector (F ID).
Example IV
1. 250mL of 1 ml/L sodium carbonate solution is added into a three-neck flask, 15 g of ZSM-5 molecular sieve is weighed and added into the three-neck flask, the mixture is stirred for 6 hours at 40 ℃, the mixture is centrifuged and washed to be neutral by deionized water, and the mixture is dried in an oven at 100 ℃ for 10 hours to obtain the pretreated molecular sieve.
2. The pretreated molecular sieve was added to 250mL of 0.06 mol/L calcium nitrate solution, stirred for 4h at 40℃and then centrifuged and washed to neutrality with deionized water, and dried in an oven at 100℃for 10h.
3. The dried molecular sieve was added to 0.5mol/L hydrochloric acid solution, stirred at 40℃for 3 hours, then centrifuged and washed with deionized water to neutrality, and dried in an oven at 100℃for 10 hours. And roasting the dried sample in a muffle furnace at 600 ℃ for 2 hours to obtain the metal calcium modified ZSM-5 molecular sieve catalyst.
The catalyst prepared in this example was used in the direct hydration of cyclohexene: and (3) performing catalyst performance evaluation in a high-pressure reaction kettle, weighing 7.5g of catalyst, 100g of deionized water and 50g of cyclohexene, adding into the reaction kettle, sealing the reaction kettle, introducing nitrogen to replace air in the kettle, then introducing nitrogen again to 0.5MPa, starting mechanical stirring and heating, timing after the reaction kettle is heated to 120 ℃, rapidly cooling the reaction kettle to room temperature after 4 hours of reaction, separating and taking out an oil phase, and performing product analysis by using a gas chromatography (HP-1 capillary chromatographic column) with a hydrogen flame ionization detector (F ID).
Example five
1. 100mL of 0.4 mol/L sodium metaaluminate solution is added into a three-neck flask, 15 g of ZSM-5 molecular sieve is weighed and added into the three-neck flask, the mixture is stirred for 2 hours at 70 ℃, and after centrifugation, deionized water is used for washing the mixture to be neutral, and the mixture is dried in an oven at 100 ℃ for 8 hours, so that the pretreated molecular sieve is obtained.
2. The pretreated molecular sieve was added to 100mL of 0.05 mol/L potassium nitrate solution, stirred for 2h at 70℃and then centrifuged and washed to neutrality with deionized water, and dried in an oven at 100℃for 8h.
3. The dried molecular sieve was added to 0.5mol/L hydrochloric acid solution, stirred at 80℃for 3 hours, then centrifuged and washed with deionized water to neutrality, and dried in an oven at 100℃for 8 hours. And roasting the dried sample in a muffle furnace at 500 ℃ for 4 hours to obtain the metal potassium modified ZSM-5 molecular sieve catalyst.
The catalyst prepared in this example was used in the direct hydration of cyclohexene: and (3) performing catalyst performance evaluation in a high-pressure reaction kettle, weighing 7.5g of catalyst, 100g of deionized water and 50g of cyclohexene, adding into the reaction kettle, sealing the reaction kettle, introducing nitrogen to replace air in the kettle, then introducing nitrogen again to 0.5MPa, starting mechanical stirring and heating, timing after the reaction kettle is heated to 120 ℃, rapidly cooling the reaction kettle to room temperature after 4 hours of reaction, separating and taking out an oil phase, and performing product analysis by using a gas chromatography (HP-1 capillary chromatographic column) with a hydrogen flame ionization detector (F ID).
Comparative example one
Application of unmodified ZSM-5 molecular sieve in cyclohexene direct hydration process: and (3) performing catalyst performance evaluation in a high-pressure reaction kettle, weighing 7.5g of catalyst, 100g of deionized water and 50g of cyclohexene, adding into the reaction kettle, sealing the reaction kettle, introducing nitrogen to replace air in the kettle, then introducing nitrogen again to 0.5MPa, starting mechanical stirring and heating, timing after the reaction kettle is heated to 120 ℃, rapidly cooling the reaction kettle to room temperature after 4 hours of reaction, separating and taking out an oil phase, and performing product analysis by using a gas chromatography (HP-1 capillary chromatographic column) with a hydrogen flame ionization detector (F ID).
Table 1 catalyst performance tables for the various examples
Summarizing: the ZSM-5 molecular sieve catalyst not only has a micropore-mesopore composite pore channel structure, but also has proper acid property. In the process of preparing cyclohexanol by hydration of cyclohexene, the catalyst can effectively improve the once-through conversion rate of cyclohexene on the premise of not reducing the selectivity of cyclohexanol.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The catalyst for preparing cyclohexanol by cyclohexene hydration and the preparation method thereof are characterized by comprising the following steps:
adding ZSM-5 molecular sieve into alkali solution for desilication reaction;
step two, the ZSM-5 molecular sieve treated in the step one is sequentially subjected to filtration, centrifugal separation, washing and drying treatment to obtain a pretreated molecular sieve;
and thirdly, adding the pretreated molecular sieve into a metal salt solution for ion exchange, and then sequentially filtering, centrifugally separating, washing, drying, acid treatment, filtering or centrifugally separating, washing, drying and roasting to obtain the metal modified ZSM-5 molecular sieve catalyst.
2. The catalyst for preparing cyclohexanol by cyclohexene hydration and a preparation method thereof according to claim 1, wherein the catalyst comprises the following components: in the first step, the alkali solution is inorganic alkali or organic alkali, wherein the inorganic alkali is one of sodium hydroxide, sodium carbonate, sodium bicarbonate or sodium metaaluminate, the organic alkali is tetrapropylammonium hydroxide, the concentration of the alkali solution is 0.1-1mol/L, and the mass ratio of the molecular sieve to the alkali solution is 1:5-20.
3. The catalyst for preparing cyclohexanol by cyclohexene hydration and a preparation method thereof according to claim 1, wherein the catalyst comprises the following components: in the first step, the desilication reaction is carried out at a temperature of 40-80 ℃ for 0.5-6h.
4. The catalyst for preparing cyclohexanol by cyclohexene hydration and a preparation method thereof according to claim 1, wherein the catalyst comprises the following components: and in the second step, washing and drying by deionized water to be neutral, and drying at 100 ℃ for 1-12h.
5. The catalyst for preparing cyclohexanol by cyclohexene hydration and a preparation method thereof according to claim 1, wherein the catalyst comprises the following components: in the third step, the metal salt solution is one of potassium nitrate, magnesium nitrate, calcium nitrate or cerium nitrate, and the concentration is 0.01-0.1mol/L.
6. The catalyst for preparing cyclohexanol by cyclohexene hydration and a preparation method thereof according to claim 1, wherein the catalyst comprises the following components: in the third step, the ion exchange treatment condition is that stirring is carried out for 0.5 to 4 hours at the temperature of 40 to 90 ℃, and the mass ratio of the molecular sieve to the metal salt solution is 1:2-20.
7. The catalyst for preparing cyclohexanol by cyclohexene hydration and a preparation method thereof according to claim 1, wherein the catalyst comprises the following components: in the third step, the acid treatment is carried out in 0.5mol/L hydrochloric acid solution and stirred for 3 hours at 40-80 ℃.
8. The catalyst for preparing cyclohexanol by cyclohexene hydration and a preparation method thereof according to claim 1, wherein the catalyst comprises the following components: and step three, roasting for 2-8 hours at 400-600 ℃.
9. The catalyst for preparing cyclohexanol by hydration of cyclohexene as described in 1-8, wherein the catalyst for hydration of cyclohexene can effectively improve the once-through conversion of cyclohexene.
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Citations (5)
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| CN1139662A (en) * | 1994-12-02 | 1997-01-08 | 三菱化学株式会社 | Making method for cyclohexanol |
| JPH0930999A (en) * | 1995-07-19 | 1997-02-04 | Mitsubishi Chem Corp | Hydration of olefin |
| CN104549434A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of molecular sieve for cyclohexene hydration preparation of cyclohexanol |
| CN106000450A (en) * | 2016-05-20 | 2016-10-12 | 中国天辰工程有限公司 | Preparation method of catalyst for hydrating cyclohexene |
| CN115591571A (en) * | 2022-09-29 | 2023-01-13 | 神马实业股份有限公司（Cn） | Modification method for preparing cyclohexanol HZSM-5catalyst by direct hydration of cyclohexene |
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2023
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|---|---|---|---|---|
| CN1139662A (en) * | 1994-12-02 | 1997-01-08 | 三菱化学株式会社 | Making method for cyclohexanol |
| JPH0930999A (en) * | 1995-07-19 | 1997-02-04 | Mitsubishi Chem Corp | Hydration of olefin |
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| CN106000450A (en) * | 2016-05-20 | 2016-10-12 | 中国天辰工程有限公司 | Preparation method of catalyst for hydrating cyclohexene |
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