CN113559919B - 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
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000036571 hydration Effects 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 20
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 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
- 238000003756 stirring Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 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
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 45
- 230000000694 effects Effects 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 8
- 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
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 230000008569 process Effects 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
- 230000015572 biosynthetic process Effects 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
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- 230000007423 decrease Effects 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
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class 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
- 230000006978 adaptation 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 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
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 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
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N monoethyl amine Natural products CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 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
- 230000005501 phase interface Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000036632 reaction speed 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
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/40—
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- 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
Abstract
The invention belongs to the technical fields of cyclohexene water and preparation of cyclohexene alcohol, and discloses a preparation method of an OTS-HZSM-5 molecular sieve and application of the molecular sieve in cyclohexene hydration. In the preparation method of the molecular sieve, the n-Octyl Trimethoxy Silane (OTS) is added in the preparation process by a microwave hydrothermal method. The preparation method improves the hydrophobicity of the catalyst, overcomes the limitation of hydration reaction substances, increases the contact between reactants and further improves the conversion rate.
Description
Technical Field
The invention relates to the technical field of cyclohexene water and preparation of cyclohexene alcohol, in particular to a preparation method of an OTS-HZSM-5 molecular sieve and application of the molecular sieve in cyclohexene hydration.
Background
Cyclohexanol is an intermediate for producing adipic acid, caprolactam, polyamide and other important chemical products, and has wide application. At present, most of industrial production of cyclohexanol adopts a cyclohexane oxidation method. The method has the defects of low cyclohexane single pass conversion rate, low alcohol ketone selectivity, safety, environmental protection and the like although the technology is mature. With the rise and development of green chemical industry, the preparation of cyclohexanol by cyclohexene hydration method is attracting more and more attention from researchers. The reaction is carried out in the water phase, so that the hydration reaction conversion rate is low and the yield of cyclohexanol is low due to low solubility of cyclohexene in water, low catalytic activity and the like. Therefore, a new catalyst for a hydration preparation process needs to be developed, 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, which aims to solve the technical problems of low hydration reaction conversion rate and low cyclohexanol yield in the preparation process of cyclohexanol by cyclohexene hydration reaction 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 Na 2 O、Al 2 O 3 、SiO 2 And H 2 O is stirred and mixed to obtain solution A;
(2) Slowly dripping 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 for 1-5h at 140-180 ℃;
(5) Washing the crystallized product in the step (4) to be neutral, drying and roasting to obtain an OTS-Na-ZSM-5 molecular sieve;
(6) OTS-Na-ZSM-5 molecular sieve is added in NH 4 NO 3 Hydrogen ion exchange is carried out in the solution;
(7) Washing, suction filtering, drying and roasting the product obtained in the step (6) to obtain the OTS-HZSM-5 molecular sieve.
Preferably, the Na 2 O、Al 2 O 3 、SiO 2 TPAOH and H 2 The molar ratio of O is 0.45:0.01:1.5:0.3:200.
Preferably, in the step (1), the stirring time is 20-30min. In the step (3), stirring is carried out for 12 hours at room temperature to form uniform sol.
More preferably, the specific condition in the step (4) is crystallization for 3 hours at 160 ℃.
Preferably, in step (5), specific drying conditions are: drying at 100-140 deg.C for 1-5 hr; the roasting conditions are as follows: roasting for 1-5h at 500-600 ℃. In the step (7), specific drying conditions are as follows: drying at 100-140 deg.C for 1-5 hr; the roasting conditions are as follows: roasting for 1-5h at 500-600 ℃.
As a preferenceIn the step (6), OTS-Na-ZSM-5 molecular sieve and NH 4 NO 3 The solid-to-liquid ratio of the solution was 1:30 (g/mL).
It is another object of the present invention to provide the use of OTS-HZSM-5 molecular sieves in cyclohexene hydration.
Specifically, water, molecular sieve OTS-HZSM-5 and cyclohexene are added into a reaction kettle in sequence for reaction, nitrogen is used for replacement during the reaction, the reaction temperature is 130 ℃ and 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 the liquid is separated to obtain cyclohexanol in an oil phase, and the water phase is extracted through 1, 2-dichloroethane to obtain cyclohexanol in an extraction phase. Wherein, the mol ratio of water to cyclohexene is 5:1; the mass of the molecular sieve OTS-HZSM-5 is 10wt% of the mass of water.
The molecular sieve prepared by the invention is used for cyclohexene hydration, and the nano particles are rapidly synthesized through microwave hydrothermal synthesis and have uniform morphology and narrow particle size distribution. Meanwhile, n-Octyl Trimethoxysilane (OTS) is added in the synthesis process to enlarge the pore diameter of the molecular sieve, and the hydrophobicity of the molecular sieve can be improved. Application of the hydrophobizing catalyst to the hydration system forms a Picking emulsion, greatly increasing contact with the reactants. The test result shows that the conversion rate is as high as 19.1% by the cyclohexene hydration evaluation device, and the cyclohexanol selectivity is kept at about 99%. Compared with the traditional hydrothermal method, the synthesis method is faster, cleaner and more economical, 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 is a combination of a hydrothermal method and a microwave method, and the advantages of microwaves and the hydrothermal method are fully exerted. Compared with a hydrothermal method, the microwave hydrothermal heating method is not a single conduction method any more, and under the action of an alternating electromagnetic field, polar molecules in materials are polarized and frequently turn and rub along with polarity change of the external alternating electromagnetic field, so that electromagnetic energy is converted into heat energy, therefore, the microwave heating is carried out on the basis of the molecules, different positions of reaction substances can be heated simultaneously, and the heating starts or stops along with the generation or disappearance of microwaves, and therefore, the microwave heating has the characteristics of low energy consumption, high speed, uniform heating and the like, and the synthesized product is pure, and has smaller and uniform average particle size. Even if the sample has a certain depth, the sample can be penetrated by microwaves, and each depth can be heated at the same time, so that heat conduction is avoided, 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 rapidly prepare the nano particles with narrow particle size distribution and uniform morphology, so that the synthesized product is pure, and has smaller and uniform average particle size;
secondly, n-Octyl Trimethoxy Silane (OTS) is dropwise added in the preparation process of the OTS-HZSM-5 molecular sieve, so that the aperture of the molecular sieve is enlarged on one hand; on the other hand OTS has C8 hydrophobic chains that render the molecular sieve somewhat hydrophobic.
Compared with the existing cyclohexene hydration reaction, the OTS-HZSM-5 molecular sieve is adopted to catalyze the cyclohexene hydration reaction, and the OTS-HZSM-5 hydrophobization molecular sieve provided by the invention is placed in a reaction system, and the 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 an evaluation conversion rate as high as 19.1%, and the cyclohexanol selectivity is kept about 99%, so that 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 reactants, the reaction system forms a Pickling emulsion to form an oil-in-water and water-in-oil form, 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 properly improve process parameters by referring to the content of the specification. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included herein. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
The present invention will be described in further detail with reference to specific embodiments thereof so that those skilled in the art can better understand the present invention.
Example 1 preparation of OTS-HZSM-5 molecular sieves
(1) Respectively weigh Na 2 O、Al 2 O 3 、SiO 2 And H 2 O is stirred and mixed for 25min to obtain solution A;
(2) Slowly dripping 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 12 hours to form uniform sol to obtain sol solution C; n (Na) 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(TPAOH):n(H 2 O)＝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 of the step (4), carrying out suction filtration, and washing with deionized water until the product is neutral to obtain white powder; transferring the obtained white powdery sample to a surface dish, placing the surface dish into a vacuum drying oven, setting 120 ℃, and vacuum drying for 4 hours; transferring the dried sample to a crucible, placing the crucible into a muffle furnace, setting 550 ℃, and roasting for 4 hours to remove the template agent, thereby obtaining the OTS-Na-ZSM-5 molecular sieve;
(6) OTS-Na-ZSM-5 molecular sieve was added to a bed containing 1mol/L NH 4 NO 3 In a beaker of solution, OTS-Na-ZSM-5 molecular sieve and NH 4 NO 3 The solid-liquid ratio of the solution is 1g to 30mL, and the solution is uniformly stirred to obtain solution D; will be provided withAdding the beaker of the solution D into a water bath kettle, and carrying out hydrogen exchange for 3 hours at 80 ℃;
(7) Taking out the product of the step (6), filtering and washing; then transferring the obtained white powdery sample to a surface dish, placing the surface dish into a vacuum drying oven, setting 120 ℃, and vacuum drying for 4 hours; and transferring the dried sample to a crucible, placing the crucible into a muffle furnace, setting 550 ℃, and roasting for 4 hours to obtain the OTS-HZSM-5 molecular sieve.
Example 2 preparation of OTS-HZSM-5 molecular sieves
(1) Respectively weigh Na 2 O、Al 2 O 3 、SiO 2 And H 2 O is stirred and mixed for 25min to obtain solution A;
(2) Slowly dripping 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 12 hours to form uniform sol to obtain sol solution C; n (Na) 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(TPAOH):n(H 2 O)＝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 of the step (4), carrying out suction filtration, and washing with deionized water until the product is neutral to obtain white powder; transferring the obtained white powdery sample to a surface dish, placing the surface dish into a vacuum drying oven, setting the temperature to 100 ℃, and vacuum drying for 5 hours; transferring the dried sample to a crucible, placing the crucible into a muffle furnace, setting the temperature to 500 ℃, and roasting for 5 hours to remove the template agent, thereby obtaining the OTS-Na-ZSM-5 molecular sieve;
(6) OTS-Na-ZSM-5 molecular sieve was added to a bed containing 1mol/L NH 4 NO 3 In a beaker of solution, OTS-Na-ZSM-5 molecular sieve and NH 4 NO 3 The solid-liquid ratio of the solution is 1g to 30mL, and the solution is uniformly stirred to obtain solution D; adding the beaker filled with the solution D into a water bath kettle, and carrying out hydrogen exchange for 3 hours at 80 ℃;
(7) Taking out the product of the step (6), filtering and washing; then transferring the obtained white powdery sample to a surface dish, placing the surface dish into a vacuum drying oven, setting the temperature to 100 ℃, and drying in vacuum for 5 hours; and transferring the dried sample to a crucible, placing the crucible into a muffle furnace, setting the temperature to 500 ℃, and roasting for 5 hours to obtain the OTS-HZSM-5 molecular sieve.
Example 3 preparation of OTS-HZSM-5 molecular sieves
(1) Respectively weigh Na 2 O、Al 2 O 3 、SiO 2 And H 2 O is stirred and mixed for 25min to obtain solution A;
(2) Slowly dripping 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 12 hours to form uniform sol to obtain sol solution C; n (Na) 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(TPAOH):n(H 2 O)＝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 of the step (4), carrying out suction filtration, and washing with deionized water until the product is neutral to obtain white powder; transferring the obtained white powdery sample to a surface dish, placing the surface dish into a vacuum drying oven, setting the temperature to 140 ℃, and vacuum drying for 1h; transferring the dried sample to a crucible, placing the crucible into a muffle furnace, setting 600 ℃, and roasting for 1h to remove the template agent, thereby obtaining the OTS-Na-ZSM-5 molecular sieve;
(6) OTS-Na-ZSM-5 molecular sieve was added to a bed containing 1mol/L NH 4 NO 3 In a beaker of solution, OTS-Na-ZSM-5 molecular sieve and NH 4 NO 3 The solid-liquid ratio of the solution is 1g to 30mL, and the solution is uniformly stirred to obtain solution D; adding the beaker filled with the solution D into a water bath kettle, and carrying out hydrogen exchange for 3 hours at 80 ℃;
(7) Taking out the product of the step (6), filtering and washing; then transferring the obtained white powdery sample to a surface dish, placing the surface dish into a vacuum drying oven, setting 140 ℃, and vacuum drying for 1h; and transferring the dried sample to a crucible, placing the crucible into a muffle furnace, setting the temperature to 600 ℃, and roasting for 1h to obtain the OTS-HZSM-5 molecular sieve.
EXAMPLE 4 preparation of cyclohexanol by cyclohexene hydration
Adding water, OTS-HZSM-5 molecular sieve and cyclohexene into a reaction kettle in sequence for reaction, wherein the molar ratio of water to cyclohexene is 5:1; the mass of the OTS-HZSM-5 molecular sieve is 10 percent of the mass of water, nitrogen is used for replacement during the reaction, the pressure is increased to 0.3MPa, the reaction temperature is 130 ℃, the reaction time is 4 hours, and after the reaction is finished, the reaction product is cooled in an ice water bath and subjected to solid-liquid separation 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 ethanol as an internal standard into the extraction phase and the oil phase obtained by the water phase, and analyzing by gas chromatography. Among them, the cyclohexene conversion and the cyclohexanol selectivity in the present invention are calculated 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 different Water amounts on hydration reactions
The molar ratio of the raw materials is set to be n (Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(TPAOH):n(H 2 O) =0.45:0.01:1.5:0.3:m (m set to 100, 200, 300, 400 and 500, respectively) 5 HZSM-5 molecular sieves were prepared, with the other reaction conditions being the same as in example 1. The effect of the hydrophobic OTS-HZSM-5 molecular sieves prepared with different amounts of water on cyclohexene hydration reactions was tested. The hydration reaction method was as described in example 4, and the evaluation results are shown in Table 1.
TABLE 1 Effect of hydrophobized OTS-HZSM-5 molecular sieves prepared with different Water amounts on hydration reactions
When the water quantity 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, so that the supersaturation degree of the system is increased, and a large number of crystal nuclei are formed and the average particle size is reduced; with the increase of the water quantity, the microstructure of the synthesized sample is gradually changed 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) 2 The O) =200 samples also had a better degree of dispersion, a uniform average particle size, and a significant improvement in conversion. When n (H) 2 When O) =200, the OTS-HZSM-5 molecular sieve synthesized by the microwave hydrothermal method has the optimal catalytic efficiency.
5.2 Effect of different crystallization temperatures on the Crystal Properties of OTS-HZSM-5 molecular sieves
The effect of different crystallization temperatures on the crystal properties of OTS-HZSM-5 molecular sieves was determined. The crystallization temperatures were set at 140 ℃, 150 ℃, 160 ℃, 170 ℃ and 180 ℃ for 3 hours, respectively, and the other OTS-HZSM-5 molecular sieves were prepared in the same manner as in example 1. And testing the influence of different crystallization temperatures on cyclohexene hydration reaction by the prepared hydrophobized OTS-HZSM-5 molecular sieve. Hydration method referring to example 4, the evaluation effect is shown in table 2.
TABLE 2 influence of hydrophobic OTS-HZSM-5 molecular sieves prepared at different crystallization temperatures on hydration reactions
For 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; as the crystallization temperature increases, the microscopic morphology of the microwave hydrothermal synthesis product becomes regular gradually, the average particle size becomes larger gradually, the dispersity is improved gradually, and micropores and mesopores of the sample are increased; further elevated temperatures, shrinkage of the pores within the crystal may occur resulting in a slight decrease in micropore surface area. From the results of the catalyst evaluation, the conversion was highest at a crystallization temperature of 160 ℃. Comprehensively considering 160 ℃ as the reaction crystallization temperature.
5.3 Effect of different templates on HZSM-5 molecular Screen Crystal Properties
Selecting tetraethylammonium hydroxide (TEAOH), N-Butylamine (butyl amine), N-diethyl ethylamine ((C) 2 H 5 ) 3 N) and tetrapropylammonium hydroxide (TPAOH) are used as templates to prepare the HZSM-5 molecular sieve, and other reaction conditions are the same as in example 1. The influence of the hydrophobized OTS-HZSM-5 molecular sieves prepared by different templates on cyclohexene hydration reaction is tested. The hydration reaction conditions were the same as in example 4, and the evaluation effects are shown in Table 3.
TABLE 3 Effect of hydrophobized OTS-HZSM-5 molecular sieves prepared with different templates on hydration reactions
From Table 3, the template agent type has obvious influence on the micro morphology, the dispersion degree and the average particle size of the microwave hydrothermal synthesis product. When tetraethylammonium hydroxide (TEAOH) was used as a template, the sample appeared as floc, and no regular-shape crystals appeared; with N-Butylamine (butyl amine) and N, N-diethylamine ((C) 2 H 5 ) 3 N) as a template, the sample appears as irregular solid agglomerates. When tetrapropylammonium hydroxide (TPAOH) is used as a template agent, the microscopic morphology of the sample is spherical, the dispersion degree is good, and the particle size is uniform and the specific surface area is large. The OTS-HZSM-5 molecular sieve crystal is prepared by adopting a microwave hydrothermal synthesis method, and a suitable template agent is tetrapropylammonium hydroxide (TPAOH).
5.4 Effect of different kinds of acids on the Crystal Properties of HZSM-5 molecular sieves when Hydrogen exchanged
NH is added to 4 NO 3 Equimolar substitution of nitric acid (HNO) 3 ) Hydrochloric acid (HCL), oxalic acid (H) 2 C 2 O 4 ) The method comprises the steps of carrying out a first treatment on the surface of the The other reaction conditions were the same as in example 1, the obtained OTS-HZSM-5 was subjected to hydration reaction, the reaction conditions were the same as in example 4, the effect of the hydrophobized OTS-HZSM-5 material subjected to hydrogen exchange by different acids on cyclohexene hydration reaction was tested, and the evaluation effect was shown in Table 4.
TABLE 4 Effect of different types of acids on the hydration reactions of OTS-HZSM-5 molecular sieves
The OTS-Na-ZSM-5 molecular sieve material carries out hydrogen exchange by inorganic acid and organic acid, H + Na is replaced to prepare the OTS-HZSM-5 molecular sieve. Inorganic acid (HNO) 3 HCl) capable of completely ionizing H + The organic framework in the molecular sieve material is greatly influenced, so that the collapse of the molecular sieve framework is easy to be unfavorable for the reaction; h ionized from weak organic acid (ammonium nitrate, oxalic acid) in solution + Little influence on the organic framework in the molecular sieve material and NH 4 NO 3 Ionized H in aqueous solution + Can be combined with Na in OTS-Na-ZSM-5 + And carrying out displacement reaction to obtain the OTS-HZSM-5 molecular sieve. Comprehensively consider NH 4 NO 3 The catalytic efficiency of the treated OTS-HZSM-5 molecular sieve material is the best.
5.5 effects of different hydration temperatures on hydration reactions
The OTS-HZSM-5 molecular sieve obtained in example 1 was used to catalyze the cyclohexene hydration reaction, with the same reaction conditions as in example 4, except that the hydration reaction temperature was selected differently, and the reaction temperature was selected and the reaction results are shown in table 5.
TABLE 5 influence of reaction temperature on cyclohexene hydration
Cyclohexene is hydrated into reversible exothermic reaction, the reaction temperature is increased, the effective collision among molecules is effectively increased, the reaction rate is accelerated, the cyclohexene adsorption rate and the cyclohexanol desorption rate on the surface of the catalyst are both accelerated, and the reaction conversion rate is effectively improved. 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 the reverse direction of hydration, so that the conversion rate decreases, and byproducts such as dimerization, etherification, etc. are generated. The optimal reaction temperature for catalyzing cyclohexene hydration reaction by OTS-HZSM-5 is comprehensively considered at 130 ℃.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The preparation method of the OTS-HZSM-5 molecular sieve is characterized by comprising the following steps of:
(1) Respectively Na 2 O、Al 2 O 3 、SiO 2 And H 2 O is stirred and mixed to obtain solution A;
(2) Slowly dripping 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 for 1-5h at 140-180 ℃;
(5) Washing the crystallized product in the step (4) to be neutral, drying and roasting to obtain an OTS-Na-ZSM-5 molecular sieve;
(6) OTS-Na-ZSM-5 molecular sieve is added in NH 4 NO 3 Hydrogen ion exchange is carried out in the solution;
(7) Washing, suction filtering, drying and roasting the product obtained in the step (6) to obtain an OTS-HZSM-5 molecular sieve;
the Na is 2 O、Al 2 O 3 、SiO 2 TPAOH and H 2 O0.45:0.01:1.5:0.3:200; the specific conditions in the step (4) are that crystallization is carried out for 3 hours at 160 ℃; in the step (6), OTS-Na-ZSM-5 molecular sieve and NH 4 NO 3 The solid-to-liquid ratio of the solution was 1:30g/mL.
2. The method of claim 1, wherein in step (1); the stirring time is 20-30min. In the step (3), stirring is carried out for 12 hours at room temperature to form uniform sol.
3. The method according to claim 1, wherein in the step (5), drying is performed at 100 to 140℃for 1 to 5 hours; roasting at 500-600 deg.c for 1-5 hr.
4. The method according to claim 1, wherein in the step (7), the drying is performed at 100 to 140℃for 1 to 5 hours; roasting at 500-600 deg.c for 1-5 hr.
5. Use of OTS-HZSM-5 molecular sieves prepared by the preparation method according to any of claims 1-4 in cyclohexene hydration.
6. The method according to claim 5, wherein water, molecular sieve OTS-HZSM-5 and cyclohexene are added into a reaction kettle in sequence for reaction, nitrogen is used for replacement during the reaction, the reaction temperature is 130 ℃ and the reaction time is 4 hours, after the reaction is finished, the water-oil two-phase product in the liquid is separated by solid-liquid separation after the reaction product is cooled in an ice water bath to obtain cyclohexanol in an oil phase, and the water phase is extracted by 1, 2-dichloroethane to obtain cyclohexanol in an extraction phase; wherein, the mol ratio of water to cyclohexene is 5:1; the mass of the molecular sieve OTS-HZSM-5 is 10wt% of the mass of water.
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