CN107899615A - A kind of catalyst for oriented chlorination and preparation method and application - Google Patents
A kind of catalyst for oriented chlorination and preparation method and application Download PDFInfo
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- CN107899615A CN107899615A CN201711068038.2A CN201711068038A CN107899615A CN 107899615 A CN107899615 A CN 107899615A CN 201711068038 A CN201711068038 A CN 201711068038A CN 107899615 A CN107899615 A CN 107899615A
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- catalyst
- oriented chlorination
- oriented
- chlorination
- directing agent
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Polymers C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 239000004033 plastic Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- VFDDAMINZKEUMV-UHFFFAOYSA-N benzene;fluoromethane Chemical compound FC.C1=CC=CC=C1 VFDDAMINZKEUMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 abstract description 12
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000460 chlorine Substances 0.000 description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 19
- 238000005235 decoking Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- JRSOABOYPLLBAR-UHFFFAOYSA-N 1,3-benzothiazole fluoromethane Chemical class CF.C1=CC=C2C(=C1)N=CS2 JRSOABOYPLLBAR-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- PBGKNXWGYQPUJK-UHFFFAOYSA-N 4-chloro-2-nitroaniline Chemical compound NC1=CC=C(Cl)C=C1[N+]([O-])=O PBGKNXWGYQPUJK-UHFFFAOYSA-N 0.000 description 1
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 229940007424 antimony trisulfide Drugs 0.000 description 1
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B01J35/19—
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of catalyst for oriented chlorination and preparation method and application, the catalyst for oriented chlorination is made of catalyst and directing agent, the catalyst is made of compound containing Fe and auxiliary agent, the auxiliary agent is compound containing Zn and/or compound containing Ga, and the weight ratio of the compound containing Fe and auxiliary agent is=6 9:14, the directing agent is benzothiazole type organic, and the weight ratio of the catalyst and directing agent is 1:1, Fe compounds, auxiliary agent and directing agent will be contained by weight and be uniformly mixed, feeding tablet press machine is compressing after adding plastic binder, and 2h is dried at 80 DEG C；The catalyst for oriented chlorination can improve the selectivity of product, reduce the growing amount of accessory substance, greatly improve the ratio of paracide and o-dichlorohenzene to 9.0, reduce the generation of polystream, m-dichlorobenzene is not produced, the conversion ratio of benzene is reached 100%, the conversion ratio of chlorobenzene reaches more than 95%.
Description
Technical field
The present invention relates to catalyst technical field, especially a kind of catalyst for oriented chlorination and preparation method and application.
Background technology
Paracide is used for leather anti-corrosion, pesticide, organic synthesis etc..As organic synthesis raw material, for synthetic dyestuffs
(large red-based g G and red base 3GL, reactive brilliant yellow and red R C) and pesticide intermediate, prevent as fumigating insecticide, fabric
Agent, mould inhibitor, deodorization of air agent are eaten into, 65%-70% is used to manufacture camphor ball, on a small quantity for extreme pressure lubricant, corrosion inhibitor；
It can be also used for medicine, solvent and mutagens.
At present, the preparation method of the paracide of comparative maturity mainly has two kinds, and one kind is co-production method, and another kind is benzene
Directional catalyzing chloridising.The purity of the paracide of co-production method production is not high, of poor quality；Production obtained by the directional catalyzing chloridising of benzene
Not only quality is good for product, but also high income.Benzene chlorination catalyst mainly has several classes：Metal chloride, sulfide, such as chlorination
The advantages of iron, aluminium chloride, antimony chloride, ferrous sulfide, antimony trisulfide, such catalyst is feed stock conversion height, and paracide selects
Property is poor；Metal and non-metal simple-substance catalyst, such as sulphur, iodine, iron, antimony, such catalyst need to add strong acid as targeting agent,
Such as p-chlorobenzenesulfonic acid, although para-selectivity increases, the separated difficulty of dichloride liquid is added at the same time.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of catalyst for oriented chlorination.
Another technical problem to be solved by this invention is the preparation method for providing above-mentioned catalyst for oriented chlorination.
Another technical problem to be solved by this invention is the application for providing above-mentioned catalyst for oriented chlorination.
In order to solve the above technical problems, the technical scheme is that：
A kind of catalyst for oriented chlorination, is made of catalyst and directing agent, and the catalyst is by compound containing Fe and auxiliary agent
Composition, the auxiliary agent be compound containing Zn and/or compound containing Ga, and the weight ratio of the compound containing Fe and auxiliary agent is=6-9:
1-4, the directing agent are benzothiazole type organic, and the weight ratio of the catalyst and directing agent is 1:1.
Preferably, above-mentioned catalyst for oriented chlorination, the compound containing Fe are iron chloride or ferrous sulfide.
Preferably, above-mentioned catalyst for oriented chlorination, the auxiliary agent are zinc oxide and/or gallium oxide.
Preferably, above-mentioned catalyst for oriented chlorination, the directing agent have structure shown in formula (I), wherein, R1For-
CH2Cl、-CH2F, R2For Cl, F, I,
Preferably, above-mentioned catalyst for oriented chlorination, the directing agent are the chloro- 6 methyl fluoride benzothiazoles of 2-.
The preparation method of above-mentioned catalyst for oriented chlorination, comprises the following steps that：To contain by weight Fe compounds, auxiliary agent and
Directing agent is uniformly mixed, and feeding tablet press machine is compressing after adding plastic binder, and 2h is dried at 80 DEG C.
Preferably, the preparation method of above-mentioned catalyst for oriented chlorination, the plastic binder are graphite and dust technology.
Preferably, the preparation method of above-mentioned catalyst for oriented chlorination, comprises the following steps that：Will per 0.6kg iron chloride,
0.2kg zinc oxide or gallium oxide and 0.8kg benzothiazole type organics are uniformly mixed, and add 50g graphite and the dilute nitre of 50ml
Then the material mixed feeding tablet press machine is made cylinder, is in 80 DEG C of drying in oven by acid to improve condensation effect
Can.
The application of above-mentioned catalyst for oriented chlorination, chlorination reaction is carried out using benzene or chlorobenzene as raw material in reaction kettle, orientation
The dosage of chlorination catalyst adds the catalyst for oriented chlorination 0.1kg-3kg, reaction temperature 45 for every 1 ton of benzene or chlorobenzene
DEG C -80 DEG C, pressure -0.005Mpa-0.5MPa, on this condition benzene conversion ratio 100%, chlorobenzene transformation ratio be more than 95%, product
In be free of m-dichlorobenzene, polystream is less than 1%, and paracide high selectivity is up to 90%.
The beneficial effects of the invention are as follows：
Above-mentioned catalyst for oriented chlorination, by the specific selection to directing agent, can improve the selectivity of product, reduce secondary
The growing amount of product, greatly improves the ratio of paracide and o-dichlorohenzene to 9.0, the generation of polystream is reduced, between not producing
Dichloro-benzenes, this causes the separation of two kinds of isomers to be more prone to；The addition of specific adjuvant Zn or Ga make the conversion of benzene at the same time
Rate reaches 100%, and the conversion ratio of chlorobenzene reaches more than 95%；In addition, the catalyst used in reaction process is solid phase, after reaction
Purpose separated with product is can reach by standing, filtering.
Embodiment
Directing agent used in following embodiments is the chloro- 6 methyl fluoride benzothiazoles of 2-.Fe-Zn catalyst is iron chloride
(weight ratio of iron chloride and zinc oxide is 3 to the catalyst formed with zinc oxide:1), Fe-Ga catalyst is iron chloride and gallium oxide
(weight ratio of iron chloride and gallium oxide is 4 to the catalyst of formation:1)；
The preparation method of catalyst for oriented chlorination is：By the chloro- 6 methyl fluoride benzene of iron chloride, zinc oxide or gallium oxide and 2-
And thiazole is uniformly mixed, and graphite and dust technology are added to improve condensation effect (iron chloride and graphite and the weighing body of dust technology
Product is than being 12:1:1 (g/g/ml)), cylinder then is made in the catalyst mixed feeding tablet press machine, in 80 DEG C of baking oven
Drying.
Embodiment 1
Tank reactor dischargeable capacity is 5L, and 45mol benzene is added into reaction kettle by charge pump, then adds orientation chlorine
Change catalyst, the catalyst for oriented chlorination is made of Fe-Zn catalyst 3.5g, directing agent 3.5g.
Reaction kettle is sealed, chlorine valve is opened and is passed through chlorine, by controlling being passed through in speed control reaction kettle of chlorine
Temperature is 50-75 DEG C, pressure -0.005MPa, and after question response, reaction solution samples after conventional deacidification, decoking carries out color
Spectrum analysis, containing 4% chlorobenzene, 85.7% paracide, 9.5% o-dichlorohenzene, 0.8% polystream in product, does not have in product
M-dichlorobenzene.
Embodiment 2
Tank reactor dischargeable capacity is 5L, and 45mol benzene is added into reaction kettle by charge pump, then adds orientation chlorine
Change catalyst, the catalyst for oriented chlorination is made of Fe-Ga catalyst 3.5g, directing agent 3.5g.
Reaction kettle is sealed, chlorine valve is opened and is passed through chlorine, by controlling being passed through in speed control reaction kettle of chlorine
Temperature is 50-75 DEG C, pressure -0.005MPa, and after question response, reaction solution samples after depickling, decoking carries out chromatography point
Analyse, 3.5% chlorobenzene, 86% paracide, 9.6% o-dichlorohenzene, 0.9% polystream are contained in product, two between not having in product
Chlorobenzene.
Embodiment 3
Tank reactor dischargeable capacity is 5L, and 45mol benzene is added into reaction kettle by charge pump, then adds orientation chlorine
Change catalyst, the catalyst for oriented chlorination is Fe-Zn catalyst (with embodiment 1) 3.5g, does not contain directing agent.
Reaction kettle is sealed, chlorine valve is opened and is passed through chlorine, by controlling being passed through in speed control reaction kettle of chlorine
Temperature is 50-75 DEG C, pressure -0.005MPa, and after question response, reaction solution samples after depickling, decoking carries out chromatography point
Analyse, 4% chlorobenzene, 60% paracide, 30% o-dichlorohenzene, 5% polystream, 1% m-dichlorobenzene are contained in product.
Embodiment 4
Tank reactor dischargeable capacity is 5L, and 45mol benzene is added into reaction kettle by charge pump, then adds orientation chlorine
Change catalyst, the catalyst for oriented chlorination is Fe-Ga catalyst (with embodiment 2) 3.5g, does not contain directing agent.
Reaction kettle is sealed, chlorine valve is opened and is passed through chlorine, by controlling being passed through in speed control reaction kettle of chlorine
Temperature is 50-75 DEG C, pressure -0.005MPa, and after question response, reaction solution samples after depickling, decoking carries out chromatography point
Analyse, 3.5% chlorobenzene, 61% paracide, 29% o-dichlorohenzene, 6% polystream, 0.5% m-dichlorobenzene are contained in product.
Embodiment 5
Tank reactor dischargeable capacity is 5L, and 45mol benzene is added into reaction kettle by charge pump, then adds and contains Feization
Compound is not added with directing agent and auxiliary agent, then seals reaction kettle, open chlorine valve and be passed through chlorine, pass through as catalyst 3.5g
The temperature being passed through in speed control reaction kettle for controlling chlorine is 50~75 DEG C, pressure -0.005MPa, after question response, instead
Answer liquid to be sampled after depickling, decoking and carry out chromatography, in product containing 2% benzene, 7% chlorobenzene, 50.4% paracide,
33.6% o-dichlorohenzene, 6% polystream, 1% m-dichlorobenzene.
The above-mentioned detailed description carried out with reference to embodiment to a kind of catalyst for oriented chlorination and preparation method and application,
It is illustrative rather than limited, several embodiments can be included according to limited scope, therefore do not departing from this hair
Changing and modifications under bright general plotting, should belong within protection scope of the present invention.
Claims (9)
- A kind of 1. catalyst for oriented chlorination, it is characterised in that：It is made of catalyst and directing agent, the catalyst is by chemical combination containing Fe Thing and auxiliary agent composition, the auxiliary agent is the weight ratio of compound containing Zn and/or compound containing Ga, the compound containing Fe and auxiliary agent For=6-9:1-4, the directing agent are benzothiazole type organic, and the weight ratio of the catalyst and directing agent is 1:1.
- 2. catalyst for oriented chlorination according to claim 1, it is characterised in that：The compound containing Fe is iron chloride or sulphur Change ferrous.
- 3. catalyst for oriented chlorination according to claim 1, it is characterised in that：The auxiliary agent is zinc oxide and/or oxidation Gallium.
- 4. catalyst for oriented chlorination according to claim 1, it is characterised in that：The directing agent has knot shown in formula (I) Structure, wherein, R1For-CH2Cl、-CH2F, R2For Cl, F, I,
- 5. catalyst for oriented chlorination according to claim 4, it is characterised in that：The directing agent is the chloro- 6 methyl fluoride benzene of 2- And thiazole.
- 6. the preparation method of catalyst for oriented chlorination described in claim 1, it is characterised in that：Comprise the following steps that：By weight Fe compounds, auxiliary agent and directing agent will be contained to be uniformly mixed, feeding tablet press machine is compressing after adding plastic binder, at 80 DEG C Dry 2h.
- 7. the preparation method of catalyst for oriented chlorination according to claim 6, it is characterised in that：The plastic binder is Graphite and dust technology.
- 8. the preparation method of catalyst for oriented chlorination according to claim 6, it is characterised in that：Comprise the following steps that：Will It is uniformly mixed, and adds per 0.6kg iron chloride, 0.2kg zinc oxide or the benzothiazole type organic of gallium oxide and 0.8kg Then to improve condensation effect cylinder is made, 80 in the material mixed feeding tablet press machine by 50g graphite and 50ml dust technologies DEG C drying in oven.
- 9. the application of catalyst for oriented chlorination described in claim 1, it is characterised in that：It is raw material in reaction kettle using benzene or chlorobenzene Chlorination reaction is carried out, the dosage of catalyst for oriented chlorination adds the catalyst for oriented chlorination 0.1kg- for every 1 ton of benzene or chlorobenzene 3kg, reaction temperature are 45 DEG C -80 DEG C, pressure -0.005Mpa-0.5Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711068038.2A CN107899615A (en) | 2017-11-03 | 2017-11-03 | A kind of catalyst for oriented chlorination and preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711068038.2A CN107899615A (en) | 2017-11-03 | 2017-11-03 | A kind of catalyst for oriented chlorination and preparation method and application |
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| Publication Number | Publication Date |
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| CN107899615A true CN107899615A (en) | 2018-04-13 |
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| CN201711068038.2A Pending CN107899615A (en) | 2017-11-03 | 2017-11-03 | A kind of catalyst for oriented chlorination and preparation method and application |
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