CN112705186A - 2, 5-dichlorotoluene isomerization catalyst, preparation method and application thereof - Google Patents
2, 5-dichlorotoluene isomerization catalyst, preparation method and application thereof Download PDFInfo
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- CN112705186A CN112705186A CN201911019197.2A CN201911019197A CN112705186A CN 112705186 A CN112705186 A CN 112705186A CN 201911019197 A CN201911019197 A CN 201911019197A CN 112705186 A CN112705186 A CN 112705186A
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- CN
- China
- Prior art keywords
- dichlorotoluene
- catalyst
- heteroatom
- source
- temperature
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- KFAKZJUYBOYVKA-UHFFFAOYSA-N 1,4-dichloro-2-methylbenzene Chemical compound CC1=CC(Cl)=CC=C1Cl KFAKZJUYBOYVKA-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 25
- DMEDNTFWIHCBRK-UHFFFAOYSA-N 1,3-dichloro-2-methylbenzene Chemical compound CC1=C(Cl)C=CC=C1Cl DMEDNTFWIHCBRK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- RYMMNSVHOKXTNN-UHFFFAOYSA-N 1,3-dichloro-5-methyl-benzene Natural products CC1=CC(Cl)=CC(Cl)=C1 RYMMNSVHOKXTNN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001721 carbon Chemical class 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 8
- 244000060011 Cocos nucifera Species 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- -1 5, 5-dichlorotoluene Chemical compound 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
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- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 2
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002808 molecular sieve Substances 0.000 description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000010453 quartz Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- 229910021536 Zeolite Inorganic materials 0.000 description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 12
- 239000010457 zeolite Substances 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- 239000012847 fine chemical Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910021392 nanocarbon Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 3
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 3
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- UZPZYFDULMKDMB-UHFFFAOYSA-N 1,2-dichloro-3,4-dimethylbenzene Chemical group CC1=CC=C(Cl)C(Cl)=C1C UZPZYFDULMKDMB-UHFFFAOYSA-N 0.000 description 2
- WYUIWKFIFOJVKW-UHFFFAOYSA-N 1,2-dichloro-4-methylbenzene Chemical compound CC1=CC=C(Cl)C(Cl)=C1 WYUIWKFIFOJVKW-UHFFFAOYSA-N 0.000 description 2
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 2
- MRUDNSFOFOQZDA-UHFFFAOYSA-N 2,6-dichlorobenzoic acid Chemical compound OC(=O)C1=C(Cl)C=CC=C1Cl MRUDNSFOFOQZDA-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- GWLKCPXYBLCEKC-UHFFFAOYSA-N 1,2-dichloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1Cl GWLKCPXYBLCEKC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical group ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 description 1
- JDMFXJULNGEPOI-UHFFFAOYSA-N 2,6-dichloroaniline Chemical compound NC1=C(Cl)C=CC=C1Cl JDMFXJULNGEPOI-UHFFFAOYSA-N 0.000 description 1
- DMIYKWPEFRFTPY-UHFFFAOYSA-N 2,6-dichlorobenzaldehyde Chemical compound ClC1=CC=CC(Cl)=C1C=O DMIYKWPEFRFTPY-UHFFFAOYSA-N 0.000 description 1
- KGKGSIUWJCAFPX-UHFFFAOYSA-N 2,6-dichlorothiobenzamide Chemical compound NC(=S)C1=C(Cl)C=CC=C1Cl KGKGSIUWJCAFPX-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
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- YBSXDWIAUZOFFV-UHFFFAOYSA-N n-[(2,6-dichlorophenyl)methylidene]hydroxylamine Chemical compound ON=CC1=C(Cl)C=CC=C1Cl YBSXDWIAUZOFFV-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- WJJBIYLGJUVNJX-UHFFFAOYSA-N pyrimidine-2-sulfonamide Chemical compound NS(=O)(=O)C1=NC=CC=N1 WJJBIYLGJUVNJX-UHFFFAOYSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 description 1
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- 150000003852 triazoles Chemical class 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/633—
-
- B01J35/643—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a 2, 5-dichlorotoluene isomerization catalyst, a preparation method and application thereof, wherein the catalyst comprises the following components: a heteroatom source is doped with a modified carbon source and used as a catalyst for isomerizing 2, 5-dichlorotoluene, and the content of heteroatoms is 0.1-20 wt% based on the weight of the doped 2, 5-dichlorotoluene isomerizing catalyst. The 2, 5-dichlorotoluene isomerization catalyst prepared by the method has developed pore passages, and the specific surface area of micropores is not less than 60% of the total specific surface area of the catalyst, thereby being beneficial to improving the selectivity of 2, 6-dichlorotoluene.
Description
Technical Field
The invention belongs to the field of fine chemical raw material preparation, and particularly relates to a 2, 5-dichlorotoluene isomerization catalyst, a preparation method and application thereof.
Background
2, 6-dichlorotoluene is an important fine chemical intermediate applied to the fields of medicine, pigment dye, agricultural chemical product production and the like. After chlorination and hydrolysis of side chain methyl, 2, 6-dichlorobenzaldehyde can be prepared, which is a raw material for further preparing the blue B and the 2, 6-dichlorobenzaldehyde oxime. 2, 6-dichlorotoluene is directly oxidized by methyl to obtain 2, 6-dichlorobenzoic acid, and then the 2, 6-dichlorobenzoic acid is acylated, hydroxylaminated and subjected to CO removal2The obtained 2, 6-dichloroaniline can be used for further preparing triazole pyrimidine sulfonamide herbicides TP and the like, and can be used for synthesizing medicaments such as diclofenac sodium and the like in medicine. The methyl side chain of 2, 6-dichlorotoluene can also react with NH under the action of ammoxidation catalyst3And air is further generated into 2, 6-dichlorobenzonitrile, and the compound can be directly used as a herbicide (dichlobenil), and can also be used for further synthesizing a herbicide diclofen (Chlorthi-amid) and a fluorine-containing acyl urea pesticide and the like.
From the above, 2, 6-dichlorotoluene is a substituted aromatic hydrocarbon with wide application and large using amount, and with the increasing demand of the fields of medicine, agriculture, textile, additives and the like for organic fine chemicals in China, the preparation process of 2, 6-dichlorotoluene also needs to be upgraded continuously to meet the demand of the product in China, so that the research on the preparation of 2, 6-dichlorotoluene has important practical significance and obvious economic significance.
At present, the preparation method of 2, 6-dichlorotoluene mainly comprises an o/p-nitrotoluene method, an o/p-toluenesulfonyl chloride method, a p-tert-butyltoluene chlorination method, a toluene/o-chlorotoluene chlorination method and the like, wherein the toluene/o-chlorotoluene chlorination method has the advantages of simple preparation process, less emission, lower cost and relatively higher atom utilization rate. However, a considerable amount of 2, 5-dichlorotoluene is generated in the chlorination process of toluene/o-chlorotoluene, and the utilization value of the side product is low, so that isomerization treatment is required to convert the side product into 2, 6-dichlorotoluene. The isomerization of the 2, 5-dichlorotoluene is realized by a gas phase isomerization reaction means, and the method has important significance for improving the production level of fine chemicals in China, meeting social requirements and realizing high-value utilization of organic raw materials.
In the literature and patent reports, the isomerization reaction of 2, 5-dichlorotoluene mainly uses zeolite molecular sieve or Al2O3Mainly, the H-type molecular sieve or the zeolite molecular sieve modified by metal Ag ions has better isomerization performance of 2, 5-dichlorotoluene, but the catalytic materials have certain problems: al (Al)2O3As a catalyst, the catalyst is generally considered to have weak acidity and poor selectivity, and is found to be easy to generate acid mist in practical application, corrode equipment and harm the environment and human health; the zeolite molecular sieve is used as a catalytic material with developed microporous pore passages, has larger specific surface area, strong shape-selective performance and more ideal acid distribution, but the acidity of the zeolite molecular sieve is still too high, and carbon deposition is easily inactivated by part of strong acid sites, so that the part of acid sites needs to be eliminated by post-treatment to avoid the inactivation. In addition, the zeolite molecular sieve catalyst has larger difference of micropore content along with different framework configurations, so that the pore channel structure and acidity of the zeolite molecular sieve catalyst have places to be balanced. The preparation process of the zeolite molecular sieve is also complicated, an aluminum source, a silicon source and the like are required to be mixed according to a certain proportion under corresponding conditions to prepare synthetic gel, then crystallization is carried out, the synthesized Na-type zeolite can be prepared into H-type zeolite only by ammonium exchange and roasting, the content of steps and condition control is more, unstable factors are easily generated, the addition of an organic template agent is also involved in the synthesis process of a part of zeolite, and the template agent needs to be removed after crystallization is completed, so that the cost is obviously increased. Finally, the processes from the preparation of the zeolite to the modification and the like involve the use of a large amount of water, and the sewage discharge is high, which affects the application of the zeolite molecular sieve, so that a space for further optimization still exists. The carbon-based material has the advantages of developed pore passages, stable property, environmental friendliness, wide source, low application cost and the like, can realize doping of various atoms in the carbon-based material by a simple treatment means, and generates remarkable acidity, reaction performance and electrons through dopingThe transfer performance is improved, so that the transfer performance is improved, and the transfer performance is improved, so that the transfer performance can catalyze a series of reactions including chemical catalysis, electrocatalysis and the like. After atom doping is realized, the carbon-based material can also become a solid acid material with a larger specific surface area/micropore specific surface area, so that the carbon-based material has certain isomerization performance and larger application potential.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a 2, 5-dichlorotoluene isomerization catalyst, a preparation method and application thereof aiming at the defects in the prior art, wherein the catalyst has the advantages of wide raw material source, simple and convenient preparation, developed pore channels, better reaction performance and low cost.
In order to solve the technical problems, the invention provides a 2, 5-dichlorotoluene isomerization catalyst in a first aspect, which comprises the following components:
a heteroatom and a carbon source, wherein the content of the heteroatom is 0.1-20 wt%, preferably 0.5-5 wt% based on the weight of the catalyst.
According to some embodiments of the invention, the catalyst has a particle size of 10 to 40 mesh.
According to some embodiments of the invention, the catalyst has a specific surface area of 700 to 1200m2·g-1Preferably 750 to 1000m2·g-1。
According to some embodiments of the invention, the catalyst has a specific surface area of micropores of 500 to 1100m2·g-1Preferably 550 to 900m2·g-1。
According to some embodiments of the invention, the specific surface area of the micropores is not less than 60%, preferably not less than 72% of the total specific surface area of the catalyst.
According to some embodiments of the invention, the heteroatom is one or more of group IIIA, group VA and group VIA.
According to some embodiments of the invention, the heteroatom is selected from at least one of B, Al, N, P.
According to some embodiments of the invention, the carbon source is selected from one or more of coal-based activated carbon, graphene oxide, carbon nanotubes, coconut shell activated carbon, bamboo charcoal.
According to some embodiments of the invention, the catalyst prepared by the present invention is a 2, 5-dichlorotoluene isomerization catalyst.
The second aspect of the present invention provides a method for preparing a 2, 5-dichlorotoluene isomerization catalyst, comprising the steps of:
1) treating the carbon source with alkali liquor to obtain a pretreated modified carbon source;
2) providing a heteroatom source solution, and then carrying out contact treatment on the pretreated modified carbon source and the heteroatom source solution to obtain a 2, 5-dichlorotoluene isomerization catalyst precursor;
3) and carrying out heat treatment on the 2, 5-dichlorotoluene isomerization catalyst precursor to obtain the 2, 5-dichlorotoluene isomerization catalyst.
According to some embodiments of the invention, the heteroatom source is one or more of an oxide, acid, ammonium salt, hydroxide, nitrate and halide in groups IIIA, VA, VIA, preferably selected from one or more of an oxide, acid and ammonium salt of B, Al, N, P.
According to some embodiments of the invention, the heteroatom source comprises one or more of boric acid, diboron trioxide, boron powder, trimethyl borate, tributyl borate, aluminum isopropoxide, trimethyl aluminum, aluminum hydroxide, pyridine, pyrrole, cyanamide, melamine, benzamide, acrylamide, phosphoric acid, diammonium phosphate, ammonium dihydrogen phosphate, and phosphorus pentachloride.
According to some embodiments of the invention, in step 1), the concentration of the alkali solution is 1-4 mol.L-1Preferably 1 to 2 mol. L-1。
According to some embodiments of the invention, in the step 1), the mass ratio of the alkali solution to the carbon source is 1 to 10, preferably 2.5 to 5.
According to some embodiments of the invention, in the step 1), the treatment temperature is 60-100 ℃ and the treatment time is 1-8 h.
According to some embodiments of the invention, in step 1), it is preferred that the lye is an aqueous solution of NaOH or KOH.
According to some embodiments of the present invention, the manner of treating the carbon source with the alkali solution in step 1) preferably comprises soaking, filtering, washing and drying.
According to some embodiments of the invention, in step 1), the lye treatment is followed by filtration and washing until the pH of the filtrate is 7.
According to some embodiments of the invention, in the step 1), the carbon source is dried in a constant temperature blowing drying oven at 110 ℃ for 2-8 hours after the pH is adjusted, so as to obtain the pretreated modified carbon source.
According to some embodiments of the present invention, after the pretreated modified carbon source is added to the heteroatom source solution in step 2), the 2, 5-dichlorotoluene isomerization catalyst precursor may be prepared by an equal volume impregnation/excess impregnation/hydrothermal treatment/rotary evaporation method.
According to some embodiments of the invention, in step 2), the content of the heteroatom source in the heteroatom source solution is 1 to 20 wt%, preferably 2 to 10 wt%.
According to some embodiments of the invention, in step 2), the heteroatom source solution is 1 to 20 wt%, preferably 0.5 to 4 wt% of the carbon source.
According to some embodiments of the invention, in the step 2), the contact treatment temperature is 80-220 ℃, and the contact treatment time is 2-8 h.
According to some embodiments of the present invention, in the step 2), preferably, the drying is performed after the contact treatment, more preferably, the drying temperature is 80 to 110 ℃, and the drying time is 4 to 8 hours.
According to some embodiments of the invention, in step 3), the heat treatment is performed in an inert gas atmosphere, the inert gas being selected from the group consisting of Ar, Ne and N2One or more of (a).
According to some embodiments of the present invention, in the step 3), the temperature of the heat treatment is 550 to 900 ℃ and the treatment time is 0.5 to 8 hours.
According to some embodiments of the invention, in step 3), the heat treatment is preferably carried out in a tubular reactor.
The third aspect of the invention provides a method for preparing 2, 6-dichlorotoluene by isomerizing 2, 5-dichlorotoluene, which comprises the following steps:
the catalyst according to the first aspect of the present invention or the catalyst prepared by the preparation method according to the second aspect of the present invention is contacted with 2, 5-dichlorotoluene in an inert gas atmosphere to react, and 2, 6-dichlorotoluene is produced.
According to some embodiments of the present invention, the 2, 5-dichlorotoluene isomerization catalyst is placed in a constant temperature fixed bed tubular reactor equipped with a preheated vaporizer and contacted with 2, 5-dichlorotoluene to effect reaction.
According to some embodiments of the present invention, 2, 5-dichlorotoluene isomerization catalyst particles are placed in a isothermal section of a isothermal fixed bed tubular reactor equipped with a preheated vaporizer and connected to an inert carrier gas, reaction feed 2, 5-dichlorotoluene liquid phase feed line, with the other regions of the reaction tubes being filled with quartz sand. After the reaction product flowed out of the reaction tube, it was condensed and collected with circulating cooling water and analyzed by gas chromatography.
According to some embodiments of the invention, the inert gas is selected from Ar, Ne and N2One or more of (a).
According to some embodiments of the invention, the flow rate of 2, 5-dichlorotoluene is 10 to 80mL min-1。
According to some embodiments of the invention, the liquid hourly space velocity is 0.2 to 1.0h-1。
According to some embodiments of the invention, the reaction pressure is 0.1MPa to 2MPa and the reaction temperature is 300 ℃ to 420 ℃.
According to some embodiments of the invention, the liquid hourly space velocity is the volumetric flow rate of the feedstock per volume of catalyst loaded.
According to some embodiments of the invention, preferred reaction conditions are: reaction temperature 360 ℃, N2The flow rate was 20 mL/min-1The liquid hourly space velocity is 0.44h-1Under the condition, the conversion rate of 2, 5-dichlorotoluene can reach 44.6 percent, and the selectivity of 2, 6-dichlorotoluene can reach 32.2 percent.
The invention has the beneficial effects that:
1. the doped 2, 5-dichlorotoluene isomerization catalyst is used for catalyzing 2, 5-dichlorotoluene to prepare 2, 6-dichlorotoluene for the first time, and the catalyst is simple in preparation method, wide in carbon source and low in cost.
2. The 2, 5-dichlorotoluene isomerization catalyst prepared by the method has developed pore passages, and the specific surface area of micropores is not less than 60% of the total specific surface area of the catalyst, thereby being beneficial to improving the selectivity of 2, 6-dichlorotoluene.
Drawings
FIG. 1 is a diagram of NH of 2, 5-dichlorotoluene isomerization catalysts prepared in examples 1-63-TPD characterization results.
FIG. 2 is a XRD characterization of the 2, 5-dichlorotoluene isomerization catalyst prepared in example 1-2.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
The preparation of the B-doped 2, 5-dichlorotoluene isomerization catalyst comprises the following steps:
1) adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, then carrying out suction filtration and washing, and drying for 4 hours at the temperature of 110 ℃ to obtain a pretreated modified carbon source;
2) the pretreated modified carbon source was added to a solution of 1.25 g boric acid and 23.75 ml distilled water as H3BO3The mass percentage content is 5 wt%. Fully mixing to obtain a solid-liquid mixture, loading the solid-liquid mixture into an autoclave with a polytetrafluoroethylene lining, heating the mixture for 6 hours at 180 ℃, then performing suction filtration and washing, and drying the mixture for 4 hours at 110 ℃ to obtain a precursor of the B-doped 2, 5-dichlorotoluene isomerization catalyst;
3) putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow at 60 mL/min-1Under the protective atmosphere of Ar at 2 ℃ for min-1The temperature is raised to 700 ℃ and treated at the temperature for 6 hours to obtain the B-doped 2, 5-dichlorotoluene isomerization catalyst.
Example 2
The preparation of the B-doped 2, 5-dichlorotoluene isomerization catalyst comprises the following steps:
1) adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, then carrying out suction filtration and washing, and drying for 4 hours at the temperature of 110 ℃ to obtain a pretreated modified carbon source;
2) adding the pretreated modified carbon source into a solution consisting of 2.5 g boric acid and 22.5 ml distilled water, and adding the solution into the solution to obtain a solution3BO3The mass percentage content is 10 wt%. Fully mixing to obtain a solid-liquid mixture, loading the solid-liquid mixture into an autoclave with a polytetrafluoroethylene lining, heating the mixture for 6 hours at 180 ℃, then performing suction filtration and washing, and drying the mixture for 4 hours at 110 ℃ to obtain a precursor of the B-doped 2, 5-dichlorotoluene isomerization catalyst;
3) putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow at 60 mL/min-1Under the protective atmosphere of Ar at 2 ℃ for min-1The temperature is raised to 700 ℃ and treated at the temperature for 6 hours to obtain the B-doped 2, 5-dichlorotoluene isomerization catalyst.
Example 3
The preparation method of the P-doped 2, 5-dichlorotoluene isomerization catalyst comprises the following steps:
1) adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, then carrying out suction filtration and washing, and drying for 4 hours at the temperature of 110 ℃ to obtain a pretreated modified carbon source;
2) 10 g of the pretreated modified carbon source are added to a solution of 2.5 g of phosphoric acid and 22.5 ml of distilled water as H3PO4The mass percentage content is 10 wt%. After fully mixing, loading the obtained solid-liquid mixture into an autoclave with a polytetrafluoroethylene lining, heating for 6 hours at 180 ℃, then carrying out suction filtration and washing, and drying for 4 hours at 110 ℃ to obtain a precursor of the P-doped 2, 5-dichlorotoluene isomerization catalyst;
3) putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow at 60 mL/min-1Ar protection ofAt 2 deg.C/min under atmosphere-1The temperature is raised to 700 ℃ and treated at the temperature for 6 hours to obtain the B-doped 2, 5-dichlorotoluene isomerization catalyst.
Example 4
The preparation method of the Al-doped 2, 5-dichlorotoluene isomerization catalyst comprises the following steps:
1) adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, then carrying out suction filtration and washing, and drying for 4 hours at the temperature of 110 ℃ to obtain a pretreated modified carbon source;
2) dropwise adding 10 g of pretreated modified carbon source into a mixed sol consisting of 0.75 g of aluminum isopropoxide and 12.5 ml of distilled water (calculated according to the weight percentage of the final Al accounting for 1 wt% of the whole solid acid), fully mixing, continuously and completely evaporating water in an open beaker under the conditions of room temperature and magnetic stirring, and drying the mixture at 110 ℃ for 4 hours to obtain a precursor of the Al-doped 2, 5-dichlorotoluene isomerization catalyst;
3) putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow at 60 mL/min-1Under the protective atmosphere of Ar at 2 ℃ for min-1The temperature is raised to 750 ℃ and treated at the temperature for 6 hours to obtain the Al-doped 2, 5-dichlorotoluene isomerization catalyst.
Example 5
N, B preparation of a doped 2, 5-dichlorotoluene isomerization catalyst, comprising the steps of:
1) adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, then carrying out suction filtration and washing, and drying for 4 hours at the temperature of 110 ℃ to obtain a pretreated modified carbon source;
2) dropwise adding 10 g of pretreated modified carbon source into a solution with 0.48 g of pyrrole, 0.59 g of boric acid and 14 g of absolute ethyl alcohol as solvents, fully mixing, standing at room temperature until the ethyl alcohol is completely evaporated, and then heating and drying at 80 ℃ for 2 hours to obtain N, B doped 2, 5-dichlorotoluene isomerization catalyst precursor;
3) putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow at 60 mL/min-1Under the protective atmosphere of Ar at 2 ℃ for min-1The temperature was raised to 750 ℃ and treated at this temperature for 6 hours to give N, B-doped 2, 5-dichlorotoluene isomerization catalyst.
Example 6
P, B preparation of a doped 2, 5-dichlorotoluene isomerization catalyst, comprising the steps of:
1) adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, then carrying out suction filtration and washing, and drying for 4 hours at the temperature of 110 ℃ to obtain a pretreated modified carbon source;
2) 10 g of the pretreated modified carbon source are added dropwise to a solution of 2.5 g of boric acid, 2.5 g of phosphoric acid and 20ml of distilled water as H3BO3And H3PO4The weight percentage of the components is 10 percent by weight. After fully mixing, loading the obtained solid-liquid mixture into an autoclave with a polytetrafluoroethylene lining, heating for 6 hours at 180 ℃, then carrying out suction filtration and washing, and drying for 4 hours at 110 ℃ to obtain a precursor of B, P doped 2, 5-dichlorotoluene isomerization catalyst;
3) putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow at 60 mL/min-1Under the protective atmosphere of Ar at 2 ℃ for min-1The temperature was raised to 700 c and treated at this temperature for 6 hours to give N, B-doped 2, 5-dichlorotoluene isomerization catalyst.
Examples 1-6 NH doped 2, 5-dichlorotoluene isomerization catalysts prepared3The TPD characterization results are shown in FIG. 1, and due to different doping elements and preparation methods, each sample generates obvious acidity difference. Wherein the B-doped sample has a lower acid strength than the P-doped sample, while the Al-doped sample has the lowest total acid content. FIG. 2 is a XRD characterization of selected representative examples 1 and 2, except for example 2 at 2 θThe diffraction peak of boron carbide appears between 30 and 40 degrees, and mainly takes wide diffraction peaks corresponding to (002) and (100) crystal planes of a graphite structure about 23 degrees and 42 degrees. The other samples except for example 2 were the same as example 1 in the position of the XRD diffraction peak.
Comparative example 1
The preparation of the B doped nano carbon particle solid acid catalyst comprises the following steps:
1) and adding 10 g of nano carbon particles into a solution with 0.2 g of boric acid and 15 g of absolute ethyl alcohol as solvents, fully mixing, standing at room temperature until the ethyl alcohol is completely evaporated, and heating and drying at 80 ℃ for 2 hours to obtain a precursor of the B doped nano carbon particle solid acid catalyst.
2) Putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow at 60 mL/min-1Under the protective atmosphere of Ar at 2 ℃ for min-1The temperature is raised to 750 ℃ at the temperature raising rate, and the mixture is treated for 6 hours at the temperature to obtain the B-doped nano carbon particle solid acid catalyst.
Comparative example 2
The preparation of HZSM-5 molecular sieve, HZSM-5 molecular sieve is synthesized based on hydrothermal crystallization method reported by literature, the concrete steps are as follows:
1) putting 10.0 g of deionized water into a beaker, placing magnetons, opening a magnetic stirrer, and adding 1.6 g of sodium metaaluminate and 3.3 g of sodium hydroxide under stirring to prepare a mixed solution;
2) 58.2 g of SiO are taken2Adding 30 wt% silica sol into the solution prepared in the step (1) under stirring, and then stirring for 1.5 hours to uniformly mix the sol;
3) adding 3.9 g of tetrapropyl ammonium hydroxide solution into the mixed sol prepared in the step (2), and continuing stirring for 1.5 hours after the addition is finished;
4) transferring the synthesized gel into a crystallization kettle, standing at 170 ℃ for 28 hours for hydrothermal crystallization, cooling the obtained product, performing suction filtration and washing, and drying at 110 ℃ to obtain a ZSM-5 molecular sieve containing a template agent;
5) heating the ZSM-5 molecular sieve containing the template agent to 550 ℃ at the heating rate of 4 ℃/min, and roasting at 550 ℃ for 4 hours to remove the template agent to obtain the NaZSM-5 molecular sieve;
6) and the obtained NaZSM-5 molecular sieve has NH content of 1mol/L4NH as molecular sieve in Cl solution4The Cl solution mass ratio is 1:10, the ion exchange is continuously carried out for 3 times under the condition that the treatment temperature is 80 ℃, and NH is obtained4ZSM-5 molecular sieve;
7) NH obtained4Heating the ZSM-5 molecular sieve to 480 ℃ at the heating rate of 4 ℃/min, and keeping the temperature at 480 ℃ for 4 hours to obtain the HZSM-5 molecular sieve;
8) and tabletting the HZSM-5 molecular sieve, crushing and screening 40-60-mesh particles, and taking the particles as a catalyst for the isomerization reaction of the 2, 5-dichlorotoluene.
The pore structure and elemental analysis characterization results of examples 1 to 6 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1 characterization results of pore structure and heteroatom content of doped 2, 5-dichlorotoluene isomerization catalyst prepared in different ways
HZSM-5 molecular sieve is composed of Si and Al elements only and SiO2/Al2O3＝30
As can be seen from Table 1, the ratio of the specific surface area of micropores to the total specific surface area of the catalyst was 72.34-81.63% for the catalysts prepared in examples 1-6.
Examples 7 to 14
Taking the catalysts prepared in examples 1-6 and comparative examples 1-2 as examples, the reaction temperature is 360 ℃, and N is2The flow rate was 20 mL/min-1The liquid hourly space velocity is 0.44h-1The vapor phase isomerization reaction of 2, 5-dichlorotoluene was carried out under the conditions of (1), and the influence of the preparation method and the doping element on the isomerization performance was examined, and the reaction results are shown in table 2:
TABLE 2 evaluation results of preparation of doped 2, 5-dichlorotoluene isomerization catalyst in different ways on isomerization reaction performance of 2, 5-dichlorotoluene
2,6-DCT, 2,4-DCT, 3,4-DCT and 2,3-DCT respectively represent isomers of dichlorotoluene, namely 2, 6-dichlorotoluene, 2, 4-dichlorotoluene, 3, 4-dichlorotoluene and 2, 3-dichlorotoluene; DCX represents dichloroxylene; DCB represents dichlorobenzene; CB represents chlorobenzene, the same as follows.
As can be seen from Table 2, the B-doped 2, 5-dichlorotoluene isomerization catalyst has good isomerization reaction performance of 2, 5-dichlorotoluene at a B doping amount of 0.97 wt%.
Example 15
This example illustrates the isomerization of B-doped 2, 5-dichlorotoluene catalyst prepared in example 2 under N2The flow rate was 20 mL/min-1The liquid hourly space velocity is 0.44h-1The vapor phase isomerization reaction of 2, 5-dichlorotoluene was carried out under the conditions described above, and the influence of temperature on the isomerization performance was examined, and the results of the reaction evaluation are shown in Table 3:
TABLE 3 Effect of reaction temperature on the Performance of a doped 2, 5-dichlorotoluene isomerization catalyst on 2, 5-dichlorotoluene isomerization
As can be seen from Table 3, the conversion rate before 350 ℃ is lower as the reaction temperature is increased, and the reaction conversion rate and the selectivity of 2, 6-dichlorotoluene are continuously increased as the reaction temperature is increased; further raising the reaction temperature to 370 ℃ results in a small increase in conversion but a significant decrease in selectivity to 2, 6-dichlorotoluene, and thus 350 ℃ is considered to be the most suitable reaction temperature for the gas phase isomerization of 2, 5-dichlorotoluene.
Example 16
The true bookEXAMPLES Using the B-doped 2, 5-dichlorotoluene isomerization catalyst prepared in example 2, in N2The flow rate was 20 mL/min-1The gas phase isomerization reaction of 2, 5-dichlorotoluene was carried out at a reaction temperature of 360 ℃ to examine the influence of the liquid air time rate on the isomerization performance, and the reaction evaluation results are shown in table 4:
TABLE 4 Effect of reaction temperature on the Performance of a doped 2, 5-dichlorotoluene isomerization catalyst in 2, 5-dichlorotoluene isomerization
As can be seen from Table 4, the reaction conversion rate gradually decreased with the increase of the liquid hourly space velocity, but at low liquid hourly space velocity, the selectivity of the side reaction products, particularly dichloroxylene, etc., was significantly increased, indicating that the disproportionation reaction, which is more favorable for methyl transfer, occurred at a lower liquid hourly space velocity, which is unfavorable for the isomerization reaction. Under a higher liquid hourly space velocity, the reaction conversion rate and the selectivity of the 2, 6-dichlorotoluene isomer are also obviously reduced due to insufficient retention time of the raw material 2, 5-dichlorotoluene molecules, so that the reaction time is 0.44h-1Is a more suitable liquid hourly space velocity condition.
It should be noted that the above embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
- A catalyst for isomerizing 2, 5-dichlorotoluene comprises the following components: a heteroatom and a carbon source, wherein the content of the heteroatom is 0.1-20 wt%, preferably 0.5-5 wt% based on the weight of the catalyst.
- 2. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 700 to 1200m2·g-1Preferably 750 to 1000m2·g-1(ii) a The specific surface area of the micropores of the catalyst is 500-1100 m2·g-1Preferably 550 to 900m2·g-1(ii) a The specific surface area of the micropores is not less than 60%, preferably not less than 72% of the total specific surface area of the catalyst.
- 3. Catalyst according to claim 1 or 2, characterized in that the heteroatoms are one or more of group IIIA, VA and VIA, preferably at least one of B, Al, N and P.
- 4. The catalyst according to any one of claims 1 to 3, wherein the carbon source is selected from one or more of coal-based activated carbon, graphene oxide, carbon nanotubes, coconut shell activated carbon and bamboo charcoal.
- The preparation method of the 5, 5-dichlorotoluene isomerization catalyst comprises the following steps:1) treating the carbon source with alkali liquor to obtain a pretreated modified carbon source, wherein the treatment preferably comprises soaking, filtering, washing and drying;2) providing a heteroatom source solution, and then carrying out contact treatment on the pretreated modified carbon source and the heteroatom source solution to obtain a 2, 5-dichlorotoluene isomerization catalyst precursor;3) and carrying out heat treatment on the 2, 5-dichlorotoluene isomerization catalyst precursor to obtain the 2, 5-dichlorotoluene isomerization catalyst.
- 6. The method according to claim 5, wherein the heteroatom source is one or more of oxides, acids, ammonium salts, hydroxides, nitrates and halides in groups IIIA, VA and VIA, preferably one or more selected from oxides, acids and ammonium salts of B, Al, N and P;more preferably, the heteroatom source is selected from one or more of boric acid, diboron trioxide, boron powder, trimethyl borate, tributyl borate, aluminum isopropoxide, trimethylaluminum, aluminum hydroxide, pyridine, pyrrole, cyanamide, melamine, benzamide, acrylamide, phosphoric acid, diammonium phosphate, ammonium dihydrogen phosphate, and phosphorus pentachloride.
- 7. The method according to claim 5 or 6, wherein the concentration of the alkali solution in the step 1) is 1-4 mol-L-1Preferably 1 to 2 mol. L-1Preferably, the alkali liquor is NaOH or KOH aqueous solution; and/or the mass ratio of the alkali liquor to the carbon source is 1-10, preferably 2.5-5; the treatment temperature is 60-100 ℃, and the treatment time is 1-8 h.
- 8. The method according to any one of claims 5 to 7, wherein in the step 2), the content of the heteroatom source in the heteroatom source solution is 1 to 20 wt%, preferably 2 to 10 wt%; and/or the total amount of the heteroatom source solution accounts for 1-20 wt% of the carbon source, preferably 0.5-4 wt%; and/or the contact temperature is 80-220 ℃, and/or the contact treatment time is 2-8 h,preferably, drying is carried out after the contact treatment, more preferably, the drying temperature is 80-110 ℃, and the drying time is 4-8 h;in step 3), the heat treatment is carried out in an inert gas atmosphere, preferably an inert gas selected from the group consisting of Ar, Ne and N2One or more of the above-mentioned materials, the heat treatment temperature is 550-900 ℃, and the treatment time is 0.5-8 h.
- 9. A preparation method of 2, 6-dichlorotoluene comprises the following steps:contacting the catalyst according to any one of claims 1 to 4 or the catalyst prepared by the preparation method according to any one of claims 5 to 8 with 2, 5-dichlorotoluene in an inert gas atmosphere to react and produce 2, 6-dichlorotoluene.
- 10. The method of claim 9, wherein the inert gas is selected from N2The flow rate of 2, 5-dichlorotoluene which is one or more of Ne and Ar is 10-80 mL/min-1The liquid hourly space velocity is 0.2-1.0 h-1The reaction pressure is 0.1MPa to 2MPa, and the reaction temperature is 300 ℃ to 420 ℃.
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