CN113559919A - Preparation method of OTS-HZSM-5 molecular sieve and application of molecular sieve in cyclohexene hydration - Google Patents
Preparation method of OTS-HZSM-5 molecular sieve and application of molecular sieve in cyclohexene hydration Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 82
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000036571 hydration Effects 0.000 title claims abstract description 18
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910001868 water Inorganic materials 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 2
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000000376 reactant Substances 0.000 abstract description 4
- KDDXDCZUWXOADG-UHFFFAOYSA-N cyclohexene;hydrate Chemical compound O.C1CCC=CC1 KDDXDCZUWXOADG-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 49
- 230000000694 effects Effects 0.000 description 17
- 239000011521 glass Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-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
- 230000009286 beneficial effect Effects 0.000 description 2
- GVOAXUUMYXAKOB-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN.CCCCN GVOAXUUMYXAKOB-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- -1 alcohol ketone Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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Abstract
The invention belongs to the technical field of cyclohexene hydrate and preparation of cyclohexanol, and discloses a preparation method of an OTS-HZSM-5 molecular sieve and application of the molecular sieve in cyclohexene hydrate. The molecular sieve preparation method is a microwave hydrothermal method, and n-Octyl Trimethoxysilane (OTS) is added in the preparation process. The preparation method improves the hydrophobicity of the catalyst, overcomes the limitation of hydration reactants, increases the contact between reactants and further improves the conversion rate.
Description
Technical Field
The invention relates to the technical field of cyclohexene hydration and preparation of cyclohexanol, and particularly relates to a preparation method of an OTS-HZSM-5 molecular sieve and application of the molecular sieve in cyclohexene hydration.
Background
Cyclohexanol is intermediate for producing adipic acid, caprolactam, polyamide and other important chemical products and has wide application. Currently, most of industrial production of cyclohexanol adopts a cyclohexane oxidation method. Although the technology of the method is mature, the method has the defects of low single pass conversion rate of cyclohexane, low selectivity of alcohol ketone, safety, environmental protection and the like. With the rise and development of green chemical industry, the preparation of cyclohexanol by a cyclohexene hydration method is more and more concerned by researchers. Because the reaction is carried out in a water phase, the hydration reaction conversion rate is lower and the yield of cyclohexanol is not high due to the reasons of low solubility of cyclohexene in water, low catalytic activity and the like. Therefore, the development of a new catalyst for hydration preparation process is urgently needed, the reaction efficiency is improved, and the catalyst has important theoretical and practical significance for synthesizing caprolactam by taking benzene as a raw material.
Disclosure of Invention
The invention provides a preparation method of an OTS-HZSM-5 molecular sieve, aiming at solving the technical problems of low hydration reaction conversion rate and low cyclohexanol yield in the cyclohexene hydration reaction preparation process in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of an OTS-HZSM-5 molecular sieve comprises the following steps:
(1) respectively adding Na2O、Al2O3、SiO2And H2Stirring and mixing the solution O to obtain a solution A;
(2) slowly dropping OTS into the solution A until the OTS is completely dissolved to obtain a solution B;
(3) adding a template agent TPAOH into the solution B, and stirring to form uniform sol to obtain a sol solution C;
(4) adding the sol solution C into a microwave hydrothermal kettle, and heating and crystallizing at 140-180 ℃ for 1-5 h;
(5) washing the product crystallized in the step (4) to be neutral, drying and roasting to obtain an OTS-Na-ZSM-5 molecular sieve;
(6) placing OTS-Na-ZSM-5 molecular sieve in NH4NO3Hydrogen ion exchange is carried out in the solution;
(7) and (4) washing, filtering, drying and roasting the product obtained in the step (6) to obtain the OTS-HZSM-5 molecular sieve.
Preferably, the Na is2O、Al2O3、SiO2TPAOH and H2The molar ratio of O is 0.45:0.01:1.5:0.3: 200.
Preferably, in the step (1), the stirring time is 20 to 30 min. And (3) stirring at room temperature for 12h to form uniform sol.
More preferably, the specific conditions in step (4) are crystallization at 160 ℃ for 3 hours.
Preferably, in the step (5), the specific drying conditions are as follows: drying at 100-140 ℃ for 1-5 h; the roasting conditions are as follows: roasting at 500-600 ℃ for 1-5 h. In the step (7), the specific drying conditions are as follows: drying at 100-140 ℃ for 1-5 h; the roasting conditions are as follows: roasting at 500-600 ℃ for 1-5 h.
Preferably, in step (6), OTS-Na-ZSM-5 molecular sieve is mixed with NH4NO3The solution had a solid-to-liquid ratio of 1:30 (g/mL).
Another purpose of the invention is to provide the application of the OTS-HZSM-5 molecular sieve in cyclohexene hydration.
Specifically, water, molecular sieve OTS-HZSM-5 and cyclohexene are sequentially added into a reaction kettle for reaction, nitrogen is used for replacement during the reaction, the pressure is increased to 0.3-04MPa, the reaction temperature is 130 ℃, the reaction time is 4 hours, after the reaction is finished, a reaction product is cooled in an ice-water bath, solid-liquid separation is carried out, a water-oil two-phase product in liquid is separated to obtain cyclohexanol in an oil phase, and the water phase is extracted through 1, 2-dichloroethane to obtain the cyclohexanol in an extraction phase. Wherein the molar ratio of water to cyclohexene is 5: 1; the mass of the molecular sieve OTS-HZSM-5 is 10 wt% of the mass of the water.
The molecular sieve prepared by the invention is used for cyclohexene hydration, and can be used for quickly synthesizing nano-particles with uniform shapes and narrow particle size distribution through microwave hydrothermal synthesis. Meanwhile, n-Octyltrimethoxysilane (OTS) is added in the synthesis process to enlarge the aperture of the molecular sieve and improve the hydrophobicity of the molecular sieve. The application of a hydrophobizing catalyst to the hydration system will form a Picking emulsion, greatly increasing the contact with the reactants. The test result shows that the conversion rate is up to 19.1% and the cyclohexanol selectivity is maintained at about 99% by using the cyclohexene hydration evaluation device. Compared with the traditional hydrothermal method, the synthesis method is faster, cleaner and more economic, can effectively improve the conversion rate of cyclohexene, has good application prospect, and has great theoretical and practical significance for industrial production of cyclohexanol.
Specifically, compared with the prior art, the preparation method of the OTS-HZSM-5 molecular sieve has the following beneficial effects:
firstly, the microwave hydrothermal method adopted by the invention is a combination of hydrothermal method and microwave method, and the advantages of microwave and hydrothermal method are fully exerted. Compared with a hydrothermal method, the microwave hydrothermal heating method is not a single conduction method, under the action of an alternating electromagnetic field, polar molecules in materials are polarized and frequently subjected to steering friction along with the change of the polarity of the alternating electromagnetic field, so that electromagnetic energy is converted into heat energy, the microwave heating is performed on the basis of molecules, different positions of reaction substances can be simultaneously heated, and the heating starts or stops along with the generation or disappearance of microwaves, so that the microwave heating has the characteristics of low energy consumption, high speed, uniform heating and the like, and the synthesized product is pure, small and uniform in average particle size. Even if the sample has a certain depth, the sample can be penetrated by the microwave, and each depth can be heated simultaneously, so that the heat conduction is avoided, the temperature difference is caused, and the reaction speed is greatly improved. Meanwhile, the microwave hydrothermal method has the characteristics of rapid heating, sensitive reaction and a heating system, so that the nano-particles with narrow particle size distribution and uniform morphology can be rapidly prepared. Therefore, the microwave hydrothermal preparation method adopted by the invention has the characteristics of low energy consumption, high speed, uniform heating and the like, and can quickly prepare the nano particles with narrow particle size distribution and uniform shape, so that the synthesized product is pure, and has smaller and uniform average particle size;
secondly, n-Octyltrimethoxysilane (OTS) is added dropwise in the preparation process of the OTS-HZSM-5 molecular sieve, so that the aperture of the molecular sieve is enlarged; on the other hand, the OTS has C8 hydrophobic chain, so that the molecular sieve has certain hydrophobicity.
Compared with the existing cyclohexene hydration reaction, the OTS-HZSM-5 molecular sieve is adopted to catalyze the cyclohexene hydration reaction, the OTS-HZSM-5 hydrophobic molecular sieve provided by the invention is placed in a reaction system, and a catalyst is positioned at a reaction phase interface, so that the contact area is increased, and the conversion rate is improved; test results prove that the OTS-HZSM-5 molecular sieve catalyst provided by the invention has the advantages that the evaluation conversion rate is up to 19.1%, the cyclohexanol selectivity is kept about 99%, and the catalytic efficiency is improved compared with that of the traditional process. In conclusion, the OTS-HZSM-5 molecular sieve provided by the invention overcomes the limitation of hydration reaction substances, a packing emulsion is formed in a reaction system to form oil-in-water and water-in-oil forms, the contact between reactants is increased, the conversion rate is further improved, the application prospect is good, and the method has great theoretical and practical significance for industrial production of cyclohexanol.
Detailed Description
The invention discloses a preparation method of an OTS-HZSM-5 molecular sieve and application of the molecular sieve in cyclohexene hydration, and a person skilled in the art can use the contents for reference and appropriately improve process parameters to realize the preparation method. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
EXAMPLE 1 preparation of OTS-HZSM-5 molecular sieves
(1) Separately weighing Na2O、Al2O3、SiO2And H2Stirring and mixing the solution O for 25min to obtain a solution A;
(2) slowly dropping n-Octyl Trimethoxy Silane (OTS) into the solution A until the solution A is completely dissolved to obtain a solution B;
(3) adding tetrapropylammonium hydroxide (TPAOH) into the solution B, and stirring at room temperature for 12h to form uniform sol to obtain a sol solution C; n (Na)2O):n(Al2O3):n(SiO2):n(TPAOH):n(H2O)＝0.45:0.01:1.5:0.3:200；
(4) Adding the sol solution C into a microwave hydrothermal kettle, and crystallizing for 3 hours at 160 ℃;
(5) taking out the product obtained in the step (4), carrying out suction filtration, and washing the product with deionized water until the product is neutral to obtain white powder; transferring the obtained white powdery sample to a watch glass, putting the watch glass into a vacuum drying oven, setting the temperature at 120 ℃, and carrying out vacuum drying for 4 hours; transferring the dried sample to a crucible, placing the crucible in a muffle furnace, setting the temperature at 550 ℃, and roasting for 4 hours to remove the template agent to obtain an OTS-Na-ZSM-5 molecular sieve;
(6) adding OTS-Na-ZSM-5 molecular sieve into the solution containing 1mol/L NH4NO3In a beaker of solution, OTS-Na-ZSM-5 molecular sieves with NH4NO3The solid-liquid ratio of the solution is 1g to 30mL, and the solution D is obtained after uniform stirring; adding the beaker filled with the solution D into a water bath kettle, and performing hydrogen exchange for 3 hours at 80 ℃;
(7) taking out the product in the step (6), filtering, and washing; then transferring the obtained white powdery sample to a watch glass, and putting the watch glass into a vacuum drying oven, setting the temperature at 120 ℃, and carrying out vacuum drying for 4 hours; and transferring the dried sample to a crucible, placing the crucible into a muffle furnace, setting the temperature at 550 ℃, and roasting for 4 hours to obtain the OTS-HZSM-5 molecular sieve.
EXAMPLE 2 preparation of OTS-HZSM-5 molecular sieves
(1) Separately weighing Na2O、Al2O3、SiO2And H2Stirring and mixing the solution O for 25min to obtain a solution A;
(2) slowly dropping n-Octyl Trimethoxy Silane (OTS) into the solution A until the solution A is completely dissolved to obtain a solution B;
(3) adding tetrapropylammonium hydroxide (TPAOH) into the solution B, and stirring at room temperature for 12h to form uniform sol to obtain a sol solution C; n (Na)2O):n(Al2O3):n(SiO2):n(TPAOH):n(H2O)＝0.45:0.01:1.5:0.3:200；
(4) Adding the sol solution C into a microwave hydrothermal kettle, and crystallizing for 3 hours at 160 ℃;
(5) taking out the product obtained in the step (4), carrying out suction filtration, and washing the product with deionized water until the product is neutral to obtain white powder; transferring the obtained white powdery sample to a watch glass, putting the watch glass into a vacuum drying oven, setting the temperature at 100 ℃, and carrying out vacuum drying for 5 hours; transferring the dried sample to a crucible, placing the crucible in a muffle furnace, setting the temperature at 500 ℃, and roasting for 5 hours to remove the template agent to obtain an OTS-Na-ZSM-5 molecular sieve;
(6) adding OTS-Na-ZSM-5 molecular sieve into the solution containing 1mol/L NH4NO3In a beaker of solution, OTS-Na-ZSM-5 molecular sieves with NH4NO3The solid-liquid ratio of the solution is 1g to 30mL, and the solution D is obtained after uniform stirring; adding the beaker filled with the solution D into a water bath kettle, and performing hydrogen exchange for 3 hours at 80 ℃;
(7) taking out the product in the step (6), filtering, and washing; then transferring the obtained white powdery sample to a watch glass, and putting the watch glass into a vacuum drying oven, setting the temperature at 100 ℃, and carrying out vacuum drying for 5 hours; and transferring the dried sample to a crucible, placing the crucible into a muffle furnace, setting the temperature at 500 ℃, and roasting for 5 hours to obtain the OTS-HZSM-5 molecular sieve.
EXAMPLE 3 preparation of OTS-HZSM-5 molecular sieves
(1) Separately weighing Na2O、Al2O3、SiO2And H2Stirring and mixing the solution O for 25min to obtain a solution A;
(2) slowly dropping n-Octyl Trimethoxy Silane (OTS) into the solution A until the solution A is completely dissolved to obtain a solution B;
(3) adding tetrapropylammonium hydroxide (TPAOH) into the solution B, and stirring at room temperature for 12h to form uniform sol to obtain a sol solution C; n (Na)2O):n(Al2O3):n(SiO2):n(TPAOH):n(H2O)＝0.45:0.01:1.5:0.3:200；
(4) Adding the sol solution C into a microwave hydrothermal kettle, and crystallizing for 3 hours at 160 ℃;
(5) taking out the product obtained in the step (4), carrying out suction filtration, and washing the product with deionized water until the product is neutral to obtain white powder; transferring the obtained white powdery sample to a watch glass, putting the watch glass into a vacuum drying oven, setting the temperature to be 140 ℃, and carrying out vacuum drying for 1 hour; transferring the dried sample to a crucible, placing the crucible in a muffle furnace, setting the temperature at 600 ℃, and roasting for 1h to remove the template agent to obtain an OTS-Na-ZSM-5 molecular sieve;
(6) adding OTS-Na-ZSM-5 molecular sieve into the solution containing 1mol/L NH4NO3In a beaker of solution, OTS-Na-ZSM-5 molecular sieves with NH4NO3The solid-liquid ratio of the solution is 1g to 30mL, and the solution D is obtained after uniform stirring; adding the beaker filled with the solution D into a water bath kettle, and performing hydrogen exchange for 3 hours at 80 ℃;
(7) taking out the product in the step (6), filtering, and washing; then transferring the obtained white powdery sample to a watch glass, and putting the watch glass into a vacuum drying oven, setting the temperature at 140 ℃, and carrying out vacuum drying for 1 h; and transferring the dried sample to a crucible, placing the crucible into a muffle furnace, setting the temperature at 600 ℃, and roasting for 1h to obtain the OTS-HZSM-5 molecular sieve.
Example 4 preparation of cyclohexanol by cyclohexene hydration
Adding water, an OTS-HZSM-5 molecular sieve and cyclohexene into a reaction kettle in sequence for reaction, wherein the molar ratio of the water to the cyclohexene is 5: 1; the mass of the OTS-HZSM-5 molecular sieve is 10 wt% of that of water, nitrogen is used for replacement during reaction, the pressure is increased to 0.3MPa, the reaction temperature is 130 ℃, the reaction time is 4h, and after the reaction is finished, a reaction product is cooled in an ice-water bath, and solid-liquid separation is carried out through centrifugal separation; separating the water-oil two-phase product by a separating funnel to obtain cyclohexanol in an oil phase, extracting the water phase by 1, 2-dichloroethane to obtain cyclohexanol in an extraction phase, adding the extraction phase and the oil phase obtained from the water phase into an internal standard substance ethanol respectively, and analyzing by gas chromatography. The calculation of the cyclohexene conversion rate and the cyclohexanol selectivity in the invention is disclosed as follows:
EXAMPLE 5 Effect of different reaction conditions on the preparation of OTS-HZSM-5 molecular sieves
5.1 Effect of Hydrophobized OTS-HZSM-5 molecular sieves prepared with varying amounts of Water on hydration reactions
Setting the raw material molar ratio as n (Na)2O):n(Al2O3):n(SiO2):n(TPAOH):n(H2O) ═ 0.45:0.01:1.5:0.3: m (m was set to 100, 200, 300, 400, and 500, respectively) 5 HZSM-5 molecular sieves were prepared, and other reaction conditions were the same as in example 1. And testing the influence of the hydrophobic OTS-HZSM-5 molecular sieve prepared in different water amounts on the cyclohexene hydration reaction. Method of hydration referring to example 4, the evaluation effect is shown in table 1.
TABLE 1 Effect of different amounts of Water prepared hydrophobized OTS-HZSM-5 molecular sieves on hydration reactions
When the water amount is reduced, the concentration of the template agent and the alkalinity of the system are increased, the hydrolysis of silicon and aluminum species is promoted, the supersaturation degree of the system is increased, and thus the formation of a large number of crystal nuclei and the reduction of the average particle size are realized; with the increase of the water amount, the micro-morphology of the synthesized sample gradually changes from a hexagonal prism shape to a spherical shape, so that the external specific surface area, the specific surface area and the pore volume are increased. When n (H)2The sample with O) — 200 had a good degree of dispersion and a uniform average particle diameter, and the conversion rate was also significantly improved. When n (H) is comprehensively considered2When O) is 200, the OTS-HZSM-5 molecular sieve synthesized by the microwave hydrothermal method has the best catalytic efficiency.
5.2 Effect of different crystallization temperatures on the Crystal Properties of OTS-HZSM-5 molecular sieves
And (3) determining the influence of different crystallization temperatures on the OTS-HZSM-5 molecular sieve crystal properties. The crystallization temperatures were set to 140 ℃, 150 ℃, 160 ℃, 170 ℃ and 180 ℃, respectively, and the crystallization time was 3 hours, and the preparation methods of other OTS-HZSM-5 molecular sieves were the same as in example 1. And (3) testing the influence of the prepared hydrophobic OTS-HZSM-5 molecular sieve on the cyclohexene hydration reaction at different crystallization temperatures. Hydration method referring to example 4, the evaluation effect is shown in table 2.
TABLE 2 Effect of hydrophobic OTS-HZSM-5 molecular sieves prepared at different crystallization temperatures on hydration reactions
For the crystallization temperature at low temperature, crystal nucleus formation and crystal growth are unfavorable in the synthesis process, and an HZSM-5 molecular sieve framework structure is difficult to form; with the increase of crystallization temperature, the micro-morphology of the microwave hydrothermal synthesis product gradually becomes regular, the average particle size gradually becomes larger, the dispersion degree gradually improves, and the micropores and mesopores of the sample increase; further increase in temperature may cause shrinkage of the pores within the crystal resulting in a slight decrease in the surface area of the micropores. From the catalyst evaluation results, it was found that the conversion was the highest when the crystallization temperature was 160 ℃. Comprehensively considering, selecting 160 ℃ as the reaction crystallization temperature.
5.3 Effect of different templates on HZSM-5 molecular Sieve Crystal Properties
Selecting tetraethyl ammonium hydroxide (TEAOH), N-Butylamine (Butylamine) and N, N-diethylethylamine ((C)2H5)3N) and tetrapropylammonium hydroxide (TPAOH) as templates, and the other reaction conditions were the same as in example 1. The influence of the hydrophobized OTS-HZSM-5 molecular sieve prepared by different templates on the cyclohexene hydration reaction is tested. The hydration reaction conditions were the same as in example 4, and the evaluation results are shown in Table 3.
TABLE 3 Effect of hydrophobized OTS-HZSM-5 molecular sieves prepared with different templates on hydration reactions
As can be seen from Table 3, the type of the template has a significant effect on the micro-morphology, the dispersion degree and the average particle size of the microwave hydrothermal synthesis product. When tetraethyl ammonium hydroxide (TEAOH) is used as a template agent, the sample is flocculent, and no flocculentCrystals with regular shapes are obtained; with N-Butylamine (Butylamine) and N, N-diethylethylamine ((C)2H5)3N) is a templating agent, the sample appears as an irregular solid agglomerate. When tetrapropylammonium hydroxide (TPAOH) is used as a template agent, the microscopic morphology of a sample is spherical, the dispersion degree is good, the particle size is uniform, and the specific surface area is large. The OTS-HZSM-5 molecular sieve crystal is prepared by a microwave hydrothermal synthesis method, and a more suitable template is tetrapropylammonium hydroxide (TPAOH).
5.4 Effect of different types of acids on HZSM-5 molecular Sieve Crystal Properties
Reacting NH4NO3Equimolar replacement with nitric acid (HNO) respectively3) Hydrochloric acid (HCL), oxalic acid (H)2C2O4) (ii) a The obtained OTS-HZSM-5 was subjected to hydration reaction under the same reaction conditions as in example 1 and under the same reaction conditions as in example 4, and the effect of the hydrophobized OTS-HZSM-5 material subjected to hydrogen exchange with different acids on the cyclohexene hydration reaction was examined and the evaluation effect was shown in Table 4.
TABLE 4 Effect of different types of acids on the hydration reaction of OTS-HZSM-5 molecular sieves
OTS-Na-ZSM-5 molecular sieve material is subjected to hydrogen exchange through inorganic acid and organic acid, and H+Replacing Na to prepare the OTS-HZSM-5 molecular sieve. Inorganic acid (HNO)3HCl) can be completely ionized to give H+The organic framework in the molecular sieve material is greatly influenced, so that the molecular sieve framework is easy to collapse and is not beneficial to reaction; h ionized by weak organic acid (ammonium nitrate, oxalic acid) in solution+Little influence on organic framework in molecular sieve material, NH4NO3H ionised in aqueous solution+Can be reacted with Na in OTS-Na-ZSM-5+And carrying out a displacement reaction to obtain the OTS-HZSM-5 molecular sieve. General consideration, NH4NO3The OTS-HZSM-5 molecular sieve material treated has the best catalytic efficiency.
5.5 Effect of different hydration reaction temperatures on hydration reaction
The OTS-HZSM-5 molecular sieve obtained in example 1 was used to catalyze the cyclohexene hydration reaction under the same conditions as in example 4 except that the hydration reaction temperature was selected to be different, and the reaction temperature and the reaction results are shown in Table 5.
TABLE 5 Effect of reaction temperature on cyclohexene hydration reaction
Cyclohexene hydration is a reversible exothermic reaction, the reaction temperature is increased, effective intermolecular collision is effectively increased, the reaction rate is increased, the cyclohexene adsorption rate and the cyclohexanol desorption rate on the surface of the catalyst are increased, and the reaction conversion rate is effectively increased. When the reaction temperature is too low, the molecular activity is low, and the conversion rate is not high; when the reaction temperature is too high, the reaction proceeds in a reverse direction to the hydration, so that the conversion rate is lowered, and by-products such as dimerization, etherification, etc. are generated. Comprehensively considering 130 ℃ as the optimal reaction temperature for catalyzing the cyclohexene hydration reaction by OTS-HZSM-5.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of an OTS-HZSM-5 molecular sieve is characterized by comprising the following steps:
(1) respectively adding Na2O、Al2O3、SiO2And H2Stirring and mixing the solution O to obtain a solution A;
(2) slowly dropping OTS into the solution A until the OTS is completely dissolved to obtain a solution B;
(3) adding a template agent TPAOH into the solution B, and stirring to form uniform sol to obtain a sol solution C;
(4) adding the sol solution C into a microwave hydrothermal kettle, and heating and crystallizing at 140-180 ℃ for 1-5 h;
(5) washing the product crystallized in the step (4) to be neutral, drying and roasting to obtain an OTS-Na-ZSM-5 molecular sieve;
(6) placing OTS-Na-ZSM-5 molecular sieve in NH4NO3Hydrogen ion exchange is carried out in the solution;
(7) and (4) washing, filtering, drying and roasting the product obtained in the step (6) to obtain the OTS-HZSM-5 molecular sieve.
2. The method according to claim 1, wherein the Na is2O、Al2O3、SiO2TPAOH and H2The molar ratio of O is 0.45:0.01:1.5:0.3: 200.
3. The method according to claim 1, wherein, in the step (1); the stirring time is 20-30 min. And (3) stirring at room temperature for 12h to form uniform sol.
4. The method of claim 1, wherein the specific conditions in step (4) are crystallization at 160 ℃ for 3 hours.
5. The preparation method as claimed in claim 1, wherein in the step (5), the drying is carried out at 100-140 ℃ for 1-5 h; roasting at 500-600 ℃ for 1-5 h.
6. The method of claim 1, wherein in step (6), the OTS-Na-ZSM-5 molecular sieve is mixed with NH4NO3The solution had a solid-to-liquid ratio of 1:30 (g/mL).
7. The preparation method as claimed in claim 1, wherein, in the step (7), the drying is carried out at 100-140 ℃ for 1-5 h; roasting at 500-600 ℃ for 1-5 h.
8. Use of the OTS-HZSM-5 molecular sieve prepared by the method of any one of claims 1-7 in cyclohexene hydration.
9. The application of claim 8, wherein water, molecular sieve OTS-HZSM-5 and cyclohexene are sequentially added into a reaction kettle for reaction, nitrogen is used for replacement during the reaction, the pressure is increased to 0.3-04MPa, the reaction temperature is 130 ℃, the reaction time is 4h, after the reaction is finished, the reaction product is cooled in an ice water bath, solid-liquid separation is carried out to separate a water-oil two-phase product in the liquid to obtain cyclohexanol in an oil phase, and the water phase is extracted by 1, 2-dichloroethane to obtain the cyclohexanol in an extract phase. Wherein the molar ratio of water to cyclohexene is 5: 1; the mass of the molecular sieve OTS-HZSM-5 is 10 wt% of the mass of the water.
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