CN116535287B - Synthesis method of 1, 3-pentachloropropane - Google Patents
Synthesis method of 1, 3-pentachloropropane Download PDFInfo
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- CN116535287B CN116535287B CN202310810401.2A CN202310810401A CN116535287B CN 116535287 B CN116535287 B CN 116535287B CN 202310810401 A CN202310810401 A CN 202310810401A CN 116535287 B CN116535287 B CN 116535287B
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- pentachloropropane
- inorganic salt
- composite catalyst
- containing inorganic
- carbon tetrachloride
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 28
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 8
- 238000007259 addition reaction Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- -1 3-methyl-1- (2-hydroxyethyl) imidazole tetrafluoroborate Chemical compound 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- YZFODOULAHZZHX-UHFFFAOYSA-N 2-(3-methyl-1,2-dihydroimidazol-1-ium-1-yl)ethanol;chloride Chemical compound [Cl-].CN1C[NH+](CCO)C=C1 YZFODOULAHZZHX-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 6
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 1
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 1
- FTCVHAQNWWBTIV-UHFFFAOYSA-N 1,1,1,2,2-pentachloropropane Chemical compound CC(Cl)(Cl)C(Cl)(Cl)Cl FTCVHAQNWWBTIV-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- XXPOHCUPSWQCFU-UHFFFAOYSA-N 2-(2-methyl-1h-imidazol-3-ium-3-yl)ethanol;chloride Chemical compound [Cl-].CC=1NC=C[N+]=1CCO XXPOHCUPSWQCFU-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- 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
-
- 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
- B01J31/30—Halides
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- 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 belongs to the technical field of organic chemistry, and particularly relates to a synthesis method of 1, 3-pentachloropropane. The invention provides a synthesis method of 1, 3-pentachloropropane, which comprises the following steps: taking chloroethylene and carbon tetrachloride as raw materials, and carrying out addition reaction under the action of a composite catalyst to obtain 1, 3-pentachloropropane; the composite catalyst is prepared from ionic liquid, iron-containing inorganic salt and zinc-containing inorganic salt. The synthesis method of the 1, 3-pentachloropropane provided by the invention has simple operation, can effectively improve the selectivity and the yield of the 1, 3-pentachloropropane, meanwhile, the composite catalyst adopted in the synthesis process can be recycled, so that the production cost can be effectively reduced, and the method is safe and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, and particularly relates to a synthesis method of 1, 3-pentachloropropane.
Background
1, 3-pentachloropropane (HCC-240 fa) is prepared important intermediates for 1, 3-pentafluoropropane. 1, 3-pentafluoropropane (HFC-245 fa) has very good physical properties and has quite wide application, and can be used for foaming rigid polyurethane and polyisocyanurate foam insulating plastics, and can replace CFC-11, CFC-12 and HCFC-141b to be used as foaming agents without damaging an ozone layer, as well as refrigerants, cleaning agents, heat transfer mediums, aerosol propellants and the like. HFC-245fa produced by HCC-240fa is then dehydrofluorinated to produce 1, 3-tetrafluoropropene (HFO-1234 ze) with low global warming potential (GWP value), which HFO-1234ze is considered to be a good substitute for HFC-134a and the like for blowing agents, refrigerants and aerosol propellants. 1-chloro-3, 3-trifluoropropene (HFO-1233 zd) with lower GWP value can be prepared by taking HCC-240fa and HF as raw materials through fluorination reaction, and the HFO-1233zd can be applied to the fields of foaming, refrigeration, cleaning and the like.
The Chinese patent application CN103274893A discloses a preparation method of 1, 3-pentachloropropane, which adopts iron, ferric chloride and triethyl phosphate to be added into a carbon tetrachloride tank to prepare a catalyst, and uses a phosphorus-containing catalyst for aftertreatment and environmental pollution.
Chinese patent CN1213005C discloses a method for preparing 1, 3-pentachloropropane, wherein carbon tetrachloride, vinyl chloride and a cuprous chloride/alcohol amine composite catalyst are added into a reactor to prepare pentachloropropane, the cuprous chloride and the alcohol amine in the route form a sticky semi-solid after coordination complex, the equipment is severely corroded, and the catalyst is difficult to recycle.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a synthesis method of 1, 3-pentachloropropane, the synthesis method of the invention takes chloroethylene and carbon tetrachloride as raw materials, and carries out addition reaction under the action of a catalyst to obtain 1, 3-pentachloropropane, the synthesis method of the 1, 3-pentachloropropane provided by the invention has simple operation, can effectively improve the selectivity and the yield of the 1, 3-pentachloropropane, meanwhile, the composite catalyst adopted in the synthesis process can be recycled, so that the production cost can be effectively reduced, and the method is safe and environment-friendly.
The technical scheme of the invention is as follows:
a synthesis method of 1, 3-pentachloropropane comprises the following steps: taking chloroethylene and carbon tetrachloride as raw materials, and carrying out addition reaction under the action of a composite catalyst to obtain 1, 3-pentachloropropane;
the composite catalyst is prepared from ionic liquid, iron-containing inorganic salt and zinc-containing inorganic salt.
Preferably, the preparation method of the composite catalyst comprises the following steps: under the protection of nitrogen, stirring the ionic liquid, the iron-containing inorganic salt and the zinc-containing inorganic salt for 45-52 hours at the temperature of 90-110 ℃, and filtering to obtain the composite catalyst.
Further, the preparation method of the composite catalyst comprises the following steps: under the protection of nitrogen, the ionic liquid, the iron-containing inorganic salt and the zinc-containing inorganic salt are stirred at 100 ℃ for 48 and h, and the composite catalyst is obtained after filtration.
Preferably, the molar ratio of the ionic liquid, the iron-containing inorganic salt and the zinc-containing inorganic salt is 1:1:0.2.
Preferably, the addition amount of the composite catalyst is 5% -10% of the total mass of the vinyl chloride and the carbon tetrachloride.
Further preferably, the addition amount of the composite catalyst is 6% -8% of the total mass of the vinyl chloride and the carbon tetrachloride.
Particularly preferably, the addition amount of the composite catalyst is 6% -7% of the total mass of the vinyl chloride and the carbon tetrachloride.
Preferably, the ionic liquid is 1-butyl-3-methylimidazole chloride ([ HEMIM)]Cl), 3-methyl-1- (2-hydroxyethyl) imidazole chloride ([ HEMIM)]Cl), 3-methyl-1- (2-hydroxyethyl) imidazole tetrafluoroborate ([ HEMIM)]BF 4 ) One of the following;
the CAS number of the 1-butyl-3-methylimidazole chloride ([ BMIM ] Cl) is 79917-90-1;
methyl-1- (2-hydroxyethyl) imidazole chloride ([ HEMIM ] Cl) has a CAS number of 61755-34-8;
3-methyl-1- (2-hydroxyethyl) imidazole tetrafluoroborate ([ HEMIM)]BF 4 ) Is numbered 374564-83-7.
Further preferably, the ionic liquid is one of 1-butyl-3-methylimidazole chloride ([ BMIM ] Cl) and 3-methyl-1- (2-hydroxyethyl) imidazole chloride ([ HEMIM ] Cl).
Particularly preferably, the ionic liquid is 1-butyl-3-methylimidazole chloride ([ BMIM ] Cl).
Preferably, the iron-containing inorganic salt is FeCl 2 、FeCl 3 、FeSO 4 One of them.
Further preferably, the iron-containing inorganic salt is FeCl 2 、FeCl 3 One of them.
Particularly preferably, the iron-containing inorganic salt is FeCl 2 。
Preferably, the zinc-containing inorganic salt is ZnSO 4 、ZnCl 2 、Zn(NO 3 ) 2 One of them.
Further preferably, the zinc-containing inorganic salt is ZnSO 4 、ZnCl 2 One of them.
Particularly preferably, the zinc-containing inorganic salt is ZnCl 2 。
Preferably, the reaction temperature in the addition reaction process is 80-150 ℃, the reaction pressure is 0.2-0.7 MPa, and the reaction time is 2-8 h.
Further preferably, the reaction temperature in the addition reaction process is 90-130 DEG o And C, the reaction pressure is 0.3-0.5 MPa, and the reaction time is 4-5 h.
Particularly preferably, the reaction temperature in the addition reaction process is 100-120 DEG o And C, the reaction pressure is 0.3-0.4 MPa, and the reaction time is 3-5 h.
Preferably, the molar ratio of the vinyl chloride to the carbon tetrachloride is 0.2-1.0:1.
Further preferably, the molar ratio of the vinyl chloride to the carbon tetrachloride is 0.3-1.0:1.
Particularly preferably, the molar ratio of the vinyl chloride to the carbon tetrachloride is 0.3-0.8:1.
The catalyst used in the traditional preparation of 1, 3-pentachloropropane is a chelate formed by tributyl phosphate and Fe metal salt, and although the catalyst can be dissolved in a carbon tetrachloride system, the catalyst has poor thermal stability, and can be decomposed to generate ferric salt crystals under the reaction condition of high temperature and high pressure, so that the reactivity is reduced, a pipeline is blocked, and in the separation process of subsequent products, the catalyst has low recovery efficiency and higher production cost due to poor thermal stability. The invention takes chloroethylene and carbon tetrachloride as raw materials, and reacts under the action of a composite catalyst to obtain 1, 3-pentachloropropane. The composite catalyst selected by the invention is prepared from ionic liquid, iron-containing inorganic salt and zinc-containing inorganic salt according to the molar ratio of 1:1:0.2, and the catalyst selected by the invention forms a catalyst which can be dissolved in a carbon tetrachloride system through supporting metal salt by the ionic liquid. On one hand, the ionic liquid supported metal salt catalyst has excellent thermal stability, does not decompose under the reaction condition of high temperature and high pressure, can effectively improve the recovery efficiency of the catalyst and reduce the production cost; on the other hand, the cations of the ionic salt are connected with the metal center through conjugated double bonds, the anions interact with the cations through hydrogen bonds, and the electronic structure of the active center of the metal catalyst can be changed by regulating and controlling the anions and the cations forming the ionic liquid, so that the regulation and control of the catalytic performance of the catalyst can be realized.
Compared with the prior art, the synthesis method of the 1, 3-pentachloropropane provided by the invention has the following advantages:
(1) The synthesis method of the 1, 3-pentachloropropane is simple to operate, the composite catalyst prepared from ionic liquid, iron-containing inorganic salt and zinc-containing inorganic salt according to the mol ratio of 1:1:0.2 is adopted to catalyze the chloroethylene and the carbon tetrachloride, can effectively improve the selectivity and the yield of the synthesized 1, 3-pentachloropropane.
(2) After the synthesis reaction of the invention is finished, the composite catalyst of the invention can be recovered by rectifying the reaction product, the recovery method is simple and convenient, the composite catalyst can be recycled, and the production cost can be effectively reduced.
(3) The composite catalyst of the invention does not contain corrosive substances, does not cause the loss of reaction equipment, can avoid causing environmental pollution, and is suitable for large-scale industrial production.
Detailed Description
The invention is further illustrated by the following description of specific embodiments, which are not intended to be limiting, and various modifications or improvements can be made by those skilled in the art in light of the basic idea of the invention, but are within the scope of the invention as long as they do not depart from the basic idea of the invention.
In the following examples and comparative examples, the reagents not specifically described are conventional reagents, and can be purchased from conventional reagent production and sales companies: the methods used, unless otherwise specified, are all prior art.
Example 1
The synthesis method of the 1, 3-pentachloropropane comprises the following steps:
adding vinyl chloride and carbon tetrachloride in a molar ratio of 0.2:1 under the action of a composite catalyst, wherein the reaction temperature is 80 ℃, the reaction pressure is 0.2 MPa, and the reaction time is 8 h, so as to obtain 1, 3-pentachloropropane; and carrying out gas chromatography detection analysis on the reacted materials.
The preparation method of the composite catalyst comprises the following steps: 3-methyl-1- (2-hydroxyethyl) imidazole tetrafluoroborate ([ HEMIM) was reacted under nitrogen]BF 4 ）、FeCl 3 And Zn (NO) 3 ) 2 Stirring at 90 deg.C according to the molar ratio of 1:1:0.2 for 52 h, and filtering.
The addition amount of the composite catalyst is 5% of the total mass of the chloroethylene and the carbon tetrachloride.
Example 2
The synthesis method of the 1, 3-pentachloropropane comprises the following steps:
adding chloroethylene and carbon tetrachloride in a molar ratio of 1.0:1 under the action of a composite catalyst, wherein the reaction temperature is 150 ℃, the reaction pressure is 0.7 MPa, and the reaction time is 2 h, so as to obtain 1, 3-pentachloropropane; and carrying out gas chromatography detection analysis on the reacted materials.
The preparation method of the composite catalyst comprises the following steps: 3-methyl-1- (2-hydroxyethyl) imidazole chloride ([ HEMIM) under nitrogen protection]Cl）、FeCl 2 And ZnSO 4 Stirring 45 and h at 110 ℃ according to the molar ratio of 1:1:0.2, and filtering to obtain the catalyst.
The addition amount of the composite catalyst is 10% of the total mass of the chloroethylene and the carbon tetrachloride.
Example 3
The synthesis method of the 1, 3-pentachloropropane comprises the following steps:
adding vinyl chloride and carbon tetrachloride in a molar ratio of 0.5:1 under the action of a composite catalyst, wherein the reaction temperature is 110 ℃, the reaction pressure is 0.3 MPa, the reaction time is 4.5 h, and 1, 3-pentachloropropane is obtained and the reacted materials are subjected to gas chromatography detection analysis.
The preparation method of the composite catalyst comprises the following steps: under nitrogen protection, 1-butyl-3-methylimidazole chloride ([ BMIM)]Cl)、FeCl 2 And ZnCl 2 Stirring 48 and h at 100 ℃ according to the molar ratio of 1:1:0.2, and filtering to obtain the catalyst.
The addition amount of the composite catalyst is 6% of the total mass of the chloroethylene and the carbon tetrachloride.
Comparative example 1 the comparative example 1 differs from example 3 in that 1-butyl-3-methylimidazole chloride ([ BMIM ] Cl) in the composite catalyst was replaced with tributyl phosphate, and other parameters and operations were the same as in example 3.
Comparative example 2 the difference between comparative example 2 and example 3 is that ZnCl in the composite catalyst is reacted 2 Replaced by CuSO 4 Other parameters and operations were the same as in example 3.
Comparative example 3 the difference between comparative example 3 and example 3 is that FeCl in the composite catalyst is 2 Replacement with AlCl 3 Other parameters and operations were the same as in example 3.
Test example one yield test of 1, 3-pentachloropropane produced by the Synthesis method of the present invention
The products obtained by the reaction of the synthetic methods of the embodiments 1-3 and the comparative examples 1-3 are subjected to gas chromatography detection analysis, to obtain the conversion rate of chloroethylene and the selectivity of 1, 3-pentachloropropane, and the yield of 1, 3-pentachloropropane was calculated according to the following formula: yield = conversion x selectivity, the results obtained are shown in table 1.
The materials after the synthetic reaction in the examples 1-3 and the comparative examples 1-3 are respectively subjected to rectification operation, the composite catalyst is recovered, then the recovered composite catalyst is added into a reaction system again for the synthetic reaction according to the synthetic method in the examples 1-3 and the comparative examples 1-3 respectively, and after the operation is circulated for 10 times, the gas chromatography detection analysis is carried out on the synthesized product of the 10 th time, to obtain the conversion rate of chloroethylene and the selectivity of 1, 3-pentachloropropane, and the yields of 1, 3-pentachloropropane were calculated, and the results obtained are shown in Table 1.
TABLE 1
As is clear from Table 1, the products obtained by the synthesis methods of examples 1 to 3 of the present invention were analyzed by gas chromatography, wherein example 3 had the best effect, and the selectivity of 1, 3-pentachloropropane was 99.8% and the yield was 99.7%. It can be seen that the components and the preparation method of the composite catalyst of the embodiments 1 to 3 can effectively improve the yield of the synthesized 1, 3-pentachloropropane compared with the catalyst of the comparative examples 1 to 3.
Further, after the composite catalyst prepared in the examples 1 to 3 of the present invention is continuously recovered and reused for 10 times, the selectivity of 1, 3-pentachloropropane in the example 3 can still reach 99.2%, and the yield is 98.8%, which fully indicates that the composite catalyst prepared in the present invention can be recycled. And the catalyst prepared in comparative examples 1-3 is repeatedly recovered and continuously catalyzed for 10 times by vinyl chloride and carbon tetrachloride, and then the obtained product is subjected to gas chromatographic analysis, so that the selectivity and the yield of the obtained 1, 3-pentachloropropane are reduced to different degrees.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (6)
1. A synthesis method of 1, 3-pentachloropropane, which is characterized by comprising the following steps: taking chloroethylene and carbon tetrachloride as raw materials, and carrying out addition reaction under the action of a composite catalyst to obtain 1, 3-pentachloropropane; the composite catalyst is prepared from ionic liquid, iron-containing inorganic salt and zinc-containing inorganic salt;
the ionic liquid is one of 1-butyl-3-methylimidazole chloride, 3-methyl-1- (2-hydroxyethyl) imidazole chloride and 3-methyl-1- (2-hydroxyethyl) imidazole tetrafluoroborate;
the iron-containing inorganic salt is FeCl 2 、FeCl 3 、FeSO 4 One of the following;
the zinc-containing inorganic salt is ZnSO 4 、ZnCl 2 、Zn(NO 3 ) 2 One of them.
2. The method for synthesizing 1, 3-pentachloropropane according to claim 1, wherein the preparation method of the composite catalyst is as follows: under the protection of nitrogen, stirring the ionic liquid, the iron-containing inorganic salt and the zinc-containing inorganic salt for 45-52 hours at the temperature of 90-110 ℃, and filtering to obtain the composite catalyst.
3. The method for synthesizing 1, 3-pentachloropropane according to claim 2, wherein the molar ratio of the ionic liquid, the iron-containing inorganic salt and the zinc-containing inorganic salt is 1:1:0.2.
4. The method for synthesizing 1, 3-pentachloropropane according to claim 1, wherein the addition amount of the composite catalyst is 5% -10% of the total mass of vinyl chloride and carbon tetrachloride.
5. The method for synthesizing 1, 3-pentachloropropane according to claim 1, wherein the reaction temperature in the addition reaction process is 80-150 ℃, the reaction pressure is 0.2-0.7 MPa, and the reaction time is 2-8 h.
6. The method for synthesizing 1, 3-pentachloropropane according to claim 1, wherein the molar ratio of the vinyl chloride to the carbon tetrachloride is 0.2-1.0:1.
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