CN114773146A - Method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with supported catalyst - Google Patents
Method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with supported catalyst Download PDFInfo
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- CN114773146A CN114773146A CN202210563193.6A CN202210563193A CN114773146A CN 114773146 A CN114773146 A CN 114773146A CN 202210563193 A CN202210563193 A CN 202210563193A CN 114773146 A CN114773146 A CN 114773146A
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- dichlorotoluene
- chlorotoluene
- molecular sieve
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- supported catalyst
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- WYUIWKFIFOJVKW-UHFFFAOYSA-N 1,2-dichloro-4-methylbenzene Chemical compound CC1=CC=C(Cl)C(Cl)=C1 WYUIWKFIFOJVKW-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 239000002808 molecular sieve Substances 0.000 claims abstract description 56
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002994 raw material Substances 0.000 claims abstract description 15
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 20
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 17
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 17
- 239000011973 solid acid Substances 0.000 description 14
- 238000005660 chlorination reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 230000021615 conjugation Effects 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000007513 acids Chemical class 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000000078 anti-malarial effect Effects 0.000 description 2
- 239000003430 antimalarial agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000329 molecular dynamics simulation Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- IRSVDHPYXFLLDS-UHFFFAOYSA-N 2,4-dichloro-1-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1Cl IRSVDHPYXFLLDS-UHFFFAOYSA-N 0.000 description 1
- CEOCVKWBUWKBKA-UHFFFAOYSA-N 2,4-dichlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1Cl CEOCVKWBUWKBKA-UHFFFAOYSA-N 0.000 description 1
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 1
- XGYLSRFSXKAYCR-UHFFFAOYSA-N 2-chloro-4-methylaniline Chemical compound CC1=CC=C(N)C(Cl)=C1 XGYLSRFSXKAYCR-UHFFFAOYSA-N 0.000 description 1
- ZWUSBSHBFFPRNE-UHFFFAOYSA-N 3,4-dichlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1Cl ZWUSBSHBFFPRNE-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000005590 Oxyfluorfen Substances 0.000 description 1
- OQMBBFQZGJFLBU-UHFFFAOYSA-N Oxyfluorfen Chemical compound C1=C([N+]([O-])=O)C(OCC)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 OQMBBFQZGJFLBU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- NUFNQYOELLVIPL-UHFFFAOYSA-N acifluorfen Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 NUFNQYOELLVIPL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- BGZZWXTVIYUUEY-UHFFFAOYSA-N fomesafen Chemical compound C1=C([N+]([O-])=O)C(C(=O)NS(=O)(=O)C)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 BGZZWXTVIYUUEY-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- YVQXNYOBSUPZMH-UHFFFAOYSA-N n-(2,4-diaminoquinazolin-6-yl)-n-[(3,4-dichlorophenyl)methyl]nitrous amide Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1N(N=O)CC1=CC=C(Cl)C(Cl)=C1 YVQXNYOBSUPZMH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with a supported catalyst, belonging to the technical field of chemical catalytic synthesis. After the synthesis method is finished, the conversion rate of the raw materials is 60-65%, the yield of 2, 4-dichlorotoluene is 31-32.5%, and the yield of 3, 4-dichlorotoluene is 20-22%. The ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene is 1.43 to 1.49. The method has the advantages of simple process, mild reaction conditions, good catalytic activity and good stability of the used molecular sieve supported catalyst, is easy to separate from the product, can obviously improve the yield of 2, 4-dichlorotoluene and 3, 4-dichlorotoluene, and reduces the ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene, and has high industrial application value.
Description
Technical Field
The invention relates to a method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with a supported catalyst, belonging to the technical field of chemical catalytic synthesis.
Background
Currently, 2, 4-dichlorotoluene is an important intermediate in the pharmaceutical, agrochemical and dye industries for the manufacture of 2, 4-dichlorobenzyl chloride and 2, 4-dichlorobenzoyl chloride, mainly for the manufacture of the antimalarial acidipine in the pharmaceutical industry. Meanwhile, the compound is also a good high-boiling-point organic solvent and is widely applied to pharmacy and organic synthesis. The traditional synthetic method is that 2, 4-dinitrotoluene is used as a raw material, and is subjected to iron powder or hydrogenation reduction, diazotization and catalytic chlorination; the method is gradually replaced by a p-chlorotoluene catalytic chlorination method due to the reasons of long process route, high cost, serious three wastes and the like. The chlorination reaction is a classical reaction, and the types of catalysts, reaction temperature and chlorination depth are different, so that the compositions of the obtained chlorination products are different.
3, 4-dichlorotoluene is an intermediate for medicine, pesticides, dyes and organic synthesis. The oxidation product 3, 4-dichlorobenzaldehyde is used in producing new antimalarial nitroquine; the side chain fluorinated derivatives of the alpha, alpha-trifluoro-3, 4-dichlorotoluene can be used for synthesizing herbicides oxyfluorfen, acifluorfen and fomesafen. 3, 4-dichlorotoluene is also used in the production of preservatives, insecticides and lubricants and is a good high boiling solvent. The traditional method for preparing 3, 4-DCT takes 3-chloro-4-aminotoluene as a raw material and adopts a process route of diazotization and cuprous chloride treatment. The process is long, the cost is high, and the three wastes are serious. With the improvement of separation technology, the chlorine chlorination process of p-chlorotoluene in the presence of catalyst to prepare Dichlorotoluene (DCT) attracts attention.
Antimony trichloride is one of important catalysts, and is widely applied to industries such as chemical industry, petroleum refining and pharmacy due to the good catalytic effect of antimony trichloride.
The patent (CN106753533.A) discloses a method for removing aromatics from isooctane solvent oil based on antimony trichloride, wherein isooctane solvent oil and antimony trichloride are mixed and then are fed into a reaction kettle, a catalyst carrier is added into the reaction kettle to enable aromatic hydrocarbons in the isooctane solvent oil to react with the antimony trichloride to generate chlorinated aromatic hydrocarbons with higher boiling points, the obtained mixture is further cut and fractionated after the reaction is finished, and the collected fraction is the dearomatized isooctane solvent oil.
However, the antimony trichloride catalyst has obvious disadvantages while having extremely high activity: the corrosion is strong, devices such as a reaction kettle and the like are easily damaged, and the service life of the devices is influenced; secondly, a large amount of sewage is generated when the antimony trichloride catalyst is used for polymerization production, and the environment is seriously polluted if the antimony trichloride catalyst cannot be treated in time; and thirdly, the reaction is difficult to recover, and needs to be subjected to post-treatment, otherwise, a large amount of corrosive waste is generated.
With the gradual enhancement of environmental awareness, more and more researchers are dedicated to research a green catalyst with the combined benefits and environmental protection, and the development trend of acid catalytic reaction is that the environment-friendly solid acid replaces the traditional liquid acid, so that the wide attention of people is attracted. The solid acid is a solid substance with a Bronsted acid center and a Lewis acid center, and the catalytic action of the solid acid is the important research content in the catalytic field. The solid acid center and the homogeneous catalysis acid center are consistent in nature, but the solid acid catalyst has unique advantages compared with the homogeneous acid catalyst, mainly shows that the solid acid catalyst has small corrosivity to equipment, is easy to separate and recover, has good high-temperature stability, can be activated and regenerated, reduces the discharge of waste, is convenient for chemical continuous operation, and is an environment-friendly catalyst. Since the solid acid is applied to the cracking production process, the application of the solid acid catalyst is rapidly developed, and different types of solid acid catalysts are developed, so that the solid acid catalysts can not only replace homogeneous acid catalysts, but also catalyze some reaction solid acids which cannot be catalyzed by the homogeneous acid. Many of the fine chemical synthesis reactions involve esterification, alkylation, acylation and isomerization reactions, which mostly require Lewis acids as catalysts, and the commonly used acids are liquid acids such as sulfuric acid and hydrofluoric acid, which are very corrosive and pollute the environment. The solid acid can enable a plurality of reactions which are difficult to carry out to react under milder conditions, and the generated pollution is small, and the corrosion to equipment is small.
Patent (CN 106582645.B) discloses a method for preparing isomerate diesel from syngas in the presence of a supported catalyst comprising an alumina support containing a modifier and an active component supported on the alumina support containing the modifier. Wherein the modifier is a group IVB metal component or a group IVB metal component and an alkali metal component and/or an alkaline earth metal component, and the active component is a group VIII metal component. The patent (CN 111097424.a) discloses a method for preparing 1, 5-pentanediol by liquid-phase hydrogenation based on a modified palladium-based supported catalyst, which adopts a two-step process, firstly, dimethyl glutarate is generated by esterification reaction, and secondly, 1, 5-pentanediol is generated by liquid-phase hydrogenation of dimethyl glutarate by adopting the modified palladium-based supported catalyst. In the method, hydrogen required by the reaction is provided through the liquid circulating material, and because the amount of hydrogen dissolved in the liquid is far more than that of the hydrogen required by the reaction, the active part of the catalyst is the hydrogen, so that the generation of carbon deposition can be avoided after long-time operation, the influence of the carbon deposition on the activity of the catalyst can be reduced, and the service life of the catalyst can be effectively prolonged; meanwhile, the material passing through the reactor is a single liquid phase material, and the process is easy to operate. Patent (CN 105032491.a) discloses a supported catalyst containing ionic liquid for alkylation reaction, under the protection of N2, AlCl3 and ionic liquid containing bis (perfluoroalkyl sulfonyl) imide group are mixed and heated according to the molar ratio of 1:1.5-1:2.0 to synthesize the ionic liquid with catalytic activity; under certain conditions, taking a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer as a template agent and tetraethoxysilane as a silicon source to synthesize a silicon-containing carrier of the catalyst; then the ionic liquid with catalytic activity is impregnated and loaded on a silicon-containing carrier under the vacuum condition to obtain the ionic liquid-containing supported catalyst for alkylation reaction.
The patent (CN102584522A) discloses a method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by using p-chlorotoluene, wherein the p-chlorotoluene is put into a reaction kettle, a catalyst accounting for 0.1-0.2% of the weight of the p-chlorotoluene is added, chlorine is introduced for reaction, the reaction temperature is kept at 40-60 ℃, the reaction time is 14-18 hours, when the content of the p-chlorotoluene reaches 0.5%, the reaction is finished, the chlorinated solution is subjected to reduced pressure rectification, and the 2, 4-dichlorotoluene and the 3, 4-dichlorotoluene are separated; the catalyst used in the reaction is prepared by mixing the following components in percentage by weight, mixing with silica sol, and treating at 80-120 ℃ for 4-6 hours: 30-40% of aluminum oxide and 60-70% of antimony trichloride; the dosage of the silica sol is 8-12% of the total weight of the aluminum oxide and the antimony trichloride. The conversion of the raw material was 88%, the yield of 2, 4-dichlorotoluene was 68%, and the yield of 3, 4-dichlorotoluene was 20%.
The invention aims to provide a supported catalyst for directionally chlorinating p-chlorotoluene to synthesize 2, 4-dichlorotoluene and 3, 4-dichlorotoluene. The direct p-toluene chlorination method has the advantages of wide raw material source and simple process, and can improve the selectivity of 2, 4-dichlorotoluene. The supported solid acid catalyst mainly shows that the solid acid catalyst has small corrosion to equipment, is easy to separate and recover, has good high-temperature stability, can be activated and regenerated, reduces the discharge of wastes, is convenient for chemical continuous operation, and is an environment-friendly catalyst.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with a supported catalyst. The direct toluene chlorination method has the advantages of wide raw material sources, simple process, capability of improving the selectivity of 2, 4-dichlorotoluene, small corrosion of the supported solid acid catalyst to equipment, easiness in separation and recovery, good high-temperature stability, capability of activating and regenerating, reduction in waste discharge, convenience in chemical continuous operation and environmental friendliness.
The invention relates to a method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene by using a supported catalyst, which comprises the following specific synthetic steps of:
(1) taking a four-mouth flask, and adding p-chlorotoluene;
(2) taking the prepared antimony trichloride loaded ZSM-5 type molecular sieve catalyst;
(3) adding antimony trichloride loaded ZSM-5 type molecular sieve catalyst into a four-neck flask filled with p-chlorotoluene;
(4) and (3) placing the four-neck flask in an oil bath, heating and stirring under the condition of introducing chlorine gas for reacting for 6-6.5 h, and removing the catalyst to obtain 2, 4-dichlorotoluene and 3, 4-dichlorotoluene.
Furthermore, the addition amount of the p-chlorotoluene is 95-105 g, and the addition amount of the antimony trichloride supported ZSM-5 type molecular sieve based catalyst is 3-3.5 g.
Furthermore, the p-chlorotoluene is pretreated by a 4A molecular sieve before use to remove moisture in the raw materials.
Further, the preparation steps of the antimony trichloride loaded ZSM-5 type molecular sieve catalyst are as follows:
grinding and screening a ZSM-5 type molecular sieve to the particle size of 20-40 meshes, and roasting in a muffle furnace at 500 ℃ for 3-3.5 h to obtain a molecular sieve carrier;
weighing 10-12 g of molecular sieve carrier, adding the molecular sieve carrier into a 250mL three-necked bottle, adding 80-85 mL of dry absolute ethyl alcohol solvent, refluxing under the protection of N2 to remove constant water, cooling, adding 4-4.2 g of anhydrous SbCl3, refluxing in N2 for 3-3.5 hours, and absorbing HCl generated in the reaction process by using dilute alkali liquor;
and after the reaction is finished, filtering while the reaction is hot, washing with absolute ethyl alcohol, drying in vacuum, and roasting to obtain the ZSM-5 molecular sieve supported anhydrous SbCl3 supported catalyst, and placing the catalyst in a dry and sealed conical flask for later use.
Further, the flow of chlorine gas introduced during the heating and stirring reaction in the step (4) is 7-10 mL/min.
Further, the heating temperature in the heating and stirring reaction process in the step (4) is 40-45 ℃.
By the scheme, the invention at least has the following advantages:
the invention uses a specific catalyst, adopts ZSM-5 type molecular sieve as a carrier, adopts antimony trichloride as an active component of the catalyst, and adopts Cl2For chlorinating agents, liquid-phase chlorine is usedThe oriented chlorination of p-chlorotoluene is carried out by a chemical method, during the reaction, the electronegativity of chlorine in p-chlorotoluene molecules is larger than that of carbon, so that an electron cloud of a C-Cl bond shifts to a Cl atom to polarize the molecules, which is called as a static induction effect, the electronegativity of a halogen atom is larger than that of a H atom, so that a-Cl substituent is an electron-withdrawing group to passivate a benzene ring, the induction effect is transmitted along a molecular chain and is weakened along with the increase of distance in the transmission process, and the conjugation effect refers to the mutual influence among atoms in the molecules of a conjugation system and is used as a substituent connected to the conjugation system, -CH3 methyl C atom is connected with a SP2 hybridized carbon atom to have the electricity supply property, so that the electron cloud density of the benzene ring is increased to provide the electron conjugation effect; the comprehensive result of the two effects enables halogen chlorine atoms to have an ortho-para positioning effect, but the positioning effect is not as strong as that of methyl; therefore, the 2 nd position in the p-chlorotoluene is easier to replace than the 3 rd position, the ZSM-5 molecular sieve is a new structure zeolite molecular sieve with high-silicon three-dimensional crossed straight channels, the Si/Al ratio of the molecular sieve can reach more than 50, the basic structural unit of the ZSM-5 molecular sieve consists of paired five-membered rings, no cage-shaped cavities and only channels, the channel structure of the ZSM-5 molecular sieve consists of a straight cylindrical channel with an oval cross section and a Z-shaped channel with an approximately round cross section, and according to the molecular dynamics analysis, the molecular diameter of the 3, 4-dichlorotoluene is smaller than 2, 4-dichlorotoluene, when SbCl is used as the material for preparing the high-silicon molecular sieve, the molecular diameter of the 3, 4-dichlorotoluene is smaller than that of the 3 rd position3When the catalyst is loaded in a ZSM-5 molecular sieve, 3, 4-dichlorotoluene can freely enter and exit from the inner pore canal of the molecular sieve in the contact process of the p-chlorotoluene and the catalyst, so that the selectivity of the 3, 4-dichlorotoluene is improved;
after the reaction is finished, the conversion rate of the raw materials is 60-65%, the yield of the 2, 4-dichlorotoluene is 31-32.5%, and the yield of the 3, 4-dichlorotoluene is 20-22%. The ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene is 1.43 to 1.49. The method has the advantages of simple process, mild reaction conditions, good catalytic activity and good stability of the used molecular sieve supported catalyst, is easy to separate from the product, can obviously improve the yield of 2, 4-dichlorotoluene and 3, 4-dichlorotoluene, and reduces the ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene, and has high industrial application value.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate embodiments of the present invention. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
Grinding and screening a ZSM-5 type molecular sieve to obtain a particle size of 20-40 meshes, and roasting in a muffle furnace at 500 ℃ for 3-3.5 h to obtain a molecular sieve carrier;
weighing 10-12 g of molecular sieve carrier, adding the molecular sieve carrier into a 250mL three-necked bottle, adding 80-85 mL of dry absolute ethyl alcohol solvent into the three-necked bottle, and adding the mixture into N2Refluxing under protection to remove constant amount of water, cooling, and adding 4-4.2 g of anhydrous SbCl3In N at2Carrying out medium reflux for 3-3.5 h, and absorbing HCl generated in the reaction process by using dilute alkali liquor;
filtering while hot after the reaction is finished, washing with absolute ethyl alcohol, vacuum drying and roasting to obtain a ZSM-5 type molecular sieve supported anhydrous SbCl3 supported catalyst, and placing the catalyst in a dry and sealed conical flask for later use;
taking a 500mL four-neck flask, adding 95-105 g of p-chlorotoluene, weighing 3-3.2 g of prepared ZSM-5 type molecular sieve loaded anhydrous SbCl3 supported catalyst, and adding the catalyst into the four-neck flask;
and then placing the four-neck flask in an oil bath pot, introducing chlorine at the flow rate of 7-10 mL/min, heating to 40-45 ℃, stirring for reaction for 6-6.5 hours, filtering and separating to remove the ZSM-5 molecular sieve supported anhydrous SbCl3 supported catalyst after the reaction is finished, and finally obtaining 2, 4-dichlorotoluene and 3, 4-dichlorotoluene.
Example 1
Taking a 500mL four-neck flask, adding 95g of p-chlorotoluene, taking 3.2g of ZSM-5 type molecular sieve supported anhydrous SbCl3 supported catalyst, and taking the ZSM-5 type molecular sieve supported anhydrous SbCl weighed in the above step3Adding a supported catalyst into the four-neck flask; the four-neck flask is placed in an oil bath kettle, chlorine gas is introduced at the flow rate of 7mL/min, the temperature is raised to 40 ℃, and the reaction is stirred for 6 hours.
After the reaction was completed for 6 hours, a sample was taken for analysis. The conversion of the raw material in the sample was 62.33%, the yield of 2, 4-dichlorotoluene was 32.25%, the yield of 3, 4-dichlorotoluene was 22.52%, and the ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene was 1.43.
Example 2
A500 mL four-neck flask was taken, 98g of p-chlorotoluene was added, and 3g of ZSM-5 type molecular sieve supported anhydrous SbCl was taken3Adding the 3g of ZSM-5 type molecular sieve supported anhydrous SbCl3 supported catalyst weighed in the step into the four-neck flask; the four-neck flask is placed in an oil bath kettle, chlorine gas is introduced at the flow rate of 8mL/min, the temperature is raised to 41 ℃, and the reaction is stirred for 6.5 hours.
After the reaction time of 6.5h, a sample was taken for analysis. The conversion of the raw material in the sample was 58.82%, the yield of 2, 4-dichlorotoluene was 30.99%, the yield of 3, 4-dichlorotoluene was 21.18%, and the ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene was 1.46.
Example 3
Taking a 500mL four-neck flask, adding 100g of p-chlorotoluene, taking 3g of ZSM-5 type molecular sieve loaded anhydrous SbCl3 supported catalyst, and adding the 3g of ZSM-5 type molecular sieve loaded anhydrous SbCl3 supported catalyst weighed in the step into the four-neck flask; the four-neck flask is placed in an oil bath kettle, chlorine gas is introduced at the flow rate of 9mL/min, the temperature is raised to 42 ℃, and the reaction is stirred for 6 hours.
Sampling and analyzing after the reaction is finished for 6 h. The conversion of the raw material in the sample was 60.12%, the yield of 2, 4-dichlorotoluene was 31.83%, the yield of 3, 4-dichlorotoluene was 21.45%, and the ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene was 1.48.
Example 4
Taking a 500mL four-neck flask, adding 103g of p-chlorotoluene, taking 3.1g of ZSM-5 type molecular sieve supported anhydrous SbCl3 supported catalyst, and adding 3.1g of ZSM-5 type molecular sieve supported anhydrous SbCl3 supported catalyst weighed in the above step into the four-neck flask; the four-neck flask is placed in an oil bath kettle, chlorine gas is introduced at the flow rate of 10mL/min, the temperature is raised to 45 ℃, and the reaction is stirred for 6 hours.
After the reaction was completed for 6 hours, a sample was taken for analysis. The conversion of the raw material in the sample was 58.19%, the yield of 2, 4-dichlorotoluene was 31.11%, the yield of 3, 4-dichlorotoluene was 21.09%, and the ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene was 1.47.
Comparative example
Comparative example 1: the other steps and components are the same as example 1, but the ZSM-5 type molecular sieve supported anhydrous SbCl3 supported catalyst of the invention is replaced by the conventional zirconium tetrachloride, and the preparation is carried out by reaction;
comparative example 2: the other steps and components are the same as example 1, but the ZSM-5 type molecular sieve supported anhydrous SbCl3 supported catalyst is replaced by the conventional SbCl3, and the preparation is carried out by the reaction;
comparing the reaction effects of examples 1-4 and the comparative example respectively, please see table 1 specifically;
TABLE 1 comparison of reaction results
It can be seen from the above detection results that the catalyst is not used in comparative example 1, the special catalyst of the present invention is replaced by other conventional catalysts in comparative example 2, which results in significant decrease of the final product yield and the conversion rate of the raw materials in the sample, and this confirms that the present invention uses the specific catalyst, adopts the ZSM-5 type molecular sieve as the carrier, antimony trichloride as the catalyst active component, Cl2 as the chlorinating agent, and adopts the liquid phase chlorination method to perform the directional chlorination of p-chlorotoluene, during the reaction, the electronegativity of chlorine is greater than that of carbon in the p-chlorotoluene molecule, so the electron cloud of the C-Cl bond shifts to the Cl atom, the molecule is polarized, which is called as the static induction effect, the electronegativity of the halogen atom is greater than that of the H atom, so the-Cl substituent is an electron withdrawing group, the benzene ring is passivated, the induction effect is transmitted along the molecular chain, and weakens with the distance increase in the transmission process, the conjugation effect refers to the mutual influence among atoms in the molecule of a conjugation system, and is used as a substituent group connected to the conjugation system, wherein a-CH 3 methyl C atom is connected with a carbon atom hybridized with SP2, so that the conjugation effect is realized, and the density of electron clouds of a benzene ring is increased; the comprehensive result of the two effects enables halogen chlorine atoms to have an adjacent para-positioning effect, but the positioning effect is not as strong as that of methyl; therefore, the 2 site in the p-chlorotoluene is easier to replace than the 3 site, the ZSM-5 molecular sieve is a new structure zeolite molecular sieve with high silicon three-dimensional crossed straight channels, the Si/Al ratio can reach more than 50, the basic structural unit of the ZSM-5 molecular sieve consists of five-membered rings in pairs, no cage-shaped cavity is formed, only pore channels are formed, the pore channel structure of the ZSM-5 molecular sieve consists of a straight cylindrical pore channel with an elliptic section and a Z-shaped pore channel with an approximately circular section, according to molecular dynamics analysis, the molecular diameter of 3, 4-dichlorotoluene is smaller than that of 2, 4-dichlorotoluene, when SbCl3 is loaded in ZSM-5 molecular sieve, in the contact process of the p-chlorotoluene and the catalyst, the 3, 4-dichlorotoluene can freely enter and exit from the inner pore canal of the molecular sieve, so that the selectivity of the 3, 4-dichlorotoluene is improved;
after the reaction is finished, the conversion rate of the raw materials is 60-65%, the yield of 2, 4-dichlorotoluene is 31-32.5%, and the yield of 3, 4-dichlorotoluene is 20-22%. The ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene is 1.43 to 1.49. The method has the advantages of simple process and mild reaction conditions, the used molecular sieve supported catalyst has good catalytic activity and good stability, is easy to separate from the product, can obviously improve the yield of 2, 4-dichlorotoluene and 3, 4-dichlorotoluene, and reduces the ratio of 2, 4-dichlorotoluene to 3, 4-dichlorotoluene.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (6)
1.A method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with a supported catalyst is characterized by comprising the following specific synthesis steps:
(1) taking a four-neck flask, and adding p-chlorotoluene;
(2) taking the prepared antimony trichloride loaded ZSM-5 type molecular sieve catalyst;
(3) adding antimony trichloride supported ZSM-5 type molecular sieve catalyst into a four-neck flask filled with p-chlorotoluene;
(4) and (3) placing the four-neck flask in an oil bath, heating and stirring under the condition of introducing chlorine gas, reacting for 6-6.5 hours, and removing the catalyst to obtain 2, 4-dichlorotoluene and 3, 4-dichlorotoluene.
2. The method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with the supported catalyst according to claim 1, wherein the supported catalyst comprises: the addition amount of the p-chlorotoluene is 95-105 g, and the addition amount of the antimony trichloride loaded ZSM-5 type molecular sieve catalyst is 3-3.5 g.
3. The method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with the supported catalyst according to claim 1, wherein the supported catalyst comprises: the p-chlorotoluene is pretreated by a 4A molecular sieve before use to remove water in the raw materials.
4. The method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with the supported catalyst as claimed in claim 1, wherein: the preparation method of the antimony trichloride supported ZSM-5 type molecular sieve catalyst comprises the following steps:
grinding and screening a ZSM-5 type molecular sieve to obtain a particle size of 20-40 meshes, and roasting in a muffle furnace at 500 ℃ for 3-3.5 h to obtain a molecular sieve carrier;
weighing 10-12 g of molecular sieve carrier, adding the molecular sieve carrier into a 250mL three-necked bottle, adding 80-85 mL of dry absolute ethyl alcohol solvent, refluxing under the protection of N2 to remove constant water, cooling, adding 4-4.2 g of anhydrous SbCl3, refluxing for 3-3.5 hours in N2, and absorbing HCl generated in the reaction process by using dilute alkali liquor;
and after the reaction is finished, filtering while the reaction is hot, washing with absolute ethyl alcohol, drying in vacuum, and roasting to obtain the ZSM-5 molecular sieve supported anhydrous SbCl3 supported catalyst, and placing the catalyst in a dry and sealed conical flask for later use.
5. The method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with the supported catalyst as claimed in claim 1, wherein: and (5) introducing chlorine gas at a flow rate of 7-10 mL/min in the heating and stirring reaction process in the step (4).
6. The method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with the supported catalyst according to claim 1, wherein the supported catalyst comprises: the heating temperature in the heating and stirring reaction process in the step (4) is 40-45 ℃.
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| CN102584522A (en) * | 2012-02-21 | 2012-07-18 | 南通市东昌化工有限公司 | Production method of 2,4-dichlorotoluene |
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| CN104945223A (en) * | 2015-06-19 | 2015-09-30 | 江苏大学 | Method for catalyzing methylbenzene to compound orthochlorotoluene through supported molecular sieves |
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