CN116986966B - Method for continuously preparing 1, 3-pentachloropropane - Google Patents
Method for continuously preparing 1, 3-pentachloropropane Download PDFInfo
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- CN116986966B CN116986966B CN202311219362.5A CN202311219362A CN116986966B CN 116986966 B CN116986966 B CN 116986966B CN 202311219362 A CN202311219362 A CN 202311219362A CN 116986966 B CN116986966 B CN 116986966B
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- ionic liquid
- pentachloropropane
- iron
- supported
- silica gel
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002608 ionic liquid Substances 0.000 claims abstract description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000741 silica gel Substances 0.000 claims abstract description 26
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000009471 action Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 239000000499 gel Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- -1 1-butyl-3-methylimidazole tetrafluoroborate Chemical compound 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 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
- 230000032683 aging Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 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 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010924 continuous production Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 9
- 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
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 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
- 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
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- RLRHXLXCAWJBGX-UHFFFAOYSA-N 2-chloro-1,3-dimethyl-1,2-dihydroimidazol-1-ium;chloride Chemical group [Cl-].CN1C=C[NH+](C)C1Cl RLRHXLXCAWJBGX-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 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
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 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
- 238000003912 environmental pollution Methods 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
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000008301 phosphite esters Chemical class 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
- 238000005057 refrigeration Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-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
- B01J31/0292—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 immobilised on a substrate
- B01J31/0295—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 immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic chemistry, and particularly relates to a method for continuously preparing 1, 3-pentachloropropane. The invention provides a method for continuously preparing 1, 3-pentachloropropane, which adopts a tubular fixed bed reactor, takes chloroethylene and carbon tetrachloride as raw materials, and (3) carrying out reaction under the action of an ionic liquid catalyst of silica gel immobilized supported iron, and continuously preparing the 1, 3-pentachloropropane. The method for continuously preparing the 1, 3-pentachloropropane can realize rapid, efficient and continuous reaction, save time and cost, has simple reaction equipment, can improve the operation efficiency, the prepared ionic liquid catalyst of the silica gel immobilized supported iron has excellent catalytic performance and thermal stability, can effectively improve the catalytic efficiency and improves the selectivity of 1, 3-pentachloropropane.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, and particularly relates to a method for continuously preparing 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.
Chinese patent application CN101913980A discloses a method for producing 1, 3-pentachloropropane, using carbon tetrachloride and chloroethylene as raw materials, continuously reacting in a tubular reactor to synthesize 1, 3-pentachloropropane, the adopted catalyst is liquid composed of main catalyst ferrous chloride and cocatalyst phosphate or phosphite esters, and the volume of the reactor is smaller than that of a kettle reactor under the same productivity. However, the method adopts ferrous chloride with unstable properties as a main catalyst, and meanwhile, in the process of activating residual liquid containing the main catalyst and a cocatalyst, fine iron powder is very likely to suspend in a circulating product stream, so that the iron powder is easy to deposit in a pipeline, and the follow-up rectification operation and the product yield can be influenced.
Chinese patent CN104513127B discloses a process for preparing 1, 3-pentachloropropane, discloses a method for synthesizing 1, 3-pentachloropropane by continuous reaction in a tubular reactor, the main catalyst is composite iron material, and the cocatalyst is phosphate or phosphite ester compound. The phosphorus will destroy the environment, so the invention inevitably brings about the problem of environmental pollution.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for preparing 1, 3-pentachloropropane by continuous reaction, which has good stability.
The technical scheme of the invention is as follows:
a process for the continuous preparation of 1, 3-pentachloropropane comprising the steps of:
the method is characterized in that a tubular fixed bed reactor is adopted, vinyl chloride and carbon tetrachloride are used as raw materials, and the reaction is carried out under the action of an ionic liquid catalyst of silica gel immobilized supported iron, so that 1, 3-pentachloropropane is continuously prepared.
Preferably, the preparation method of the silica gel immobilized supported iron ionic liquid catalyst comprises the following steps:
s1, mixing the ionic liquid and FeCl 2 Stirring under the protection of nitrogen, and filtering out insoluble matters to obtain iron-supported ionic liquid;
s2, adding a silicon source into the flask, stirring and heating to 55-65 ℃, then respectively adding the iron-supported ionic liquid obtained in the step S1 and absolute ethyl alcohol, uniformly mixing, dropwise adding a nitric acid solution with the mass concentration of 10%, standing and generating gel, and then aging for 20-30 hours at room temperature;
and S3, carrying out vacuum drying on the aged gel obtained in the step S2 to obtain the silica gel immobilized supported iron ionic liquid catalyst.
Preferably, the mass ratio of the iron-supported ionic liquid, the silicon source, the absolute ethyl alcohol and the nitric acid solution added in the reaction process of the step S2 is 1:5-15:3-10:2-8.
Further preferably, the mass ratio of the added iron-supported ionic liquid, the silicon source, the absolute ethyl alcohol and the nitric acid solution is 1: 5-10:5-8:3-5.
Particularly preferably, the mass ratio of the added iron-supported ionic liquid to the silicon source to the anhydrous ethanol to the nitric acid solution is 1:5-8:6-8:3-4.
Preferably, the ionic liquid in step S1 is 1-butyl-3-methylimidazole chloride ([ BMIM)]Cl), 1-butyl-3-methylimidazole tetrafluoroborate ([ BMIM ]]BF 4 ) 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;
the 1-butyl-3-methylimidazole tetrafluoroborate ([ BMIM)]BF 4 ) Is 174501-65-6;
the CAS number of the 3-methyl-1- (2-hydroxyethyl) imidazole chloride ([ HEMIM ] Cl) is 61755-34-8;
the 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 silicon source in the step S2 is one of ethyl orthosilicate, silica sol and water glass.
Further preferably, the silicon source is one of ethyl orthosilicate and a silica sol.
Particularly preferably, the silicon source is ethyl orthosilicate.
Preferably, in the step S1, the ionic liquid and FeCl 2 Under the protection of nitrogen, 48 and h are stirred at the temperature of 90-110 ℃.
Preferably, in the step S1, the ionic liquid and FeCl 2 The molar ratio of (2) is 1:1.
Preferably, the temperature of the vacuum drying in the step S3 is 90-110 ℃, the vacuum degree is-0.05 MPa, and the time is 10-15 hours.
Preferably, in the preparation process of the tubular fixed bed reactor, the molar ratio of the vinyl chloride to the carbon tetrachloride is 0.2-1.5:1, the reaction temperature is 80-150 ℃, the reaction pressure is 0-0.2 MPa, and the mass airspeed is 0.5-3 h -1 。
Further preferably, the molar ratio of the vinyl chloride to the carbon tetrachloride is 0.5-1.3:1, the reaction temperature is 85-130 ℃, the reaction pressure is 0.1-0.2 MPa, and the mass airspeed is 0.8-2.5 h -1 。
Particularly preferably, the molar ratio of the vinyl chloride to the carbon tetrachloride is 0.5-0.8:1, the reaction temperature is 95-120 ℃, the reaction pressure is 0.15-0.18 MPa, and the mass airspeed is 0.8-1.5 h -1 。
The invention provides a method for continuously preparing 1, 3-pentachloropropane, which adopts a tubular fixed bed reactor, vinyl chloride and carbon tetrachloride are used as raw materials to react under the action of a catalyst, and the 1, 3-pentachloropropane can be continuously prepared.
The catalyst adopted by the invention is a silica gel immobilized iron-supported ionic liquid catalyst prepared by a specific preparation process, and the immobilized ionic liquid is a solid substance with an ionic liquid structure on the surface or the load ionic liquid by fixing the ionic liquid on a certain carrier. Through immobilization, the use amount of the ionic liquid can be reduced, so that the cost is reduced, and meanwhile, the reaction is easy to continuously carry out and is easy to separate and recycle.
Further, in the prior art, since the product obtained by the reaction of vinyl chloride and carbon tetrachloride is 1, 3-pentachloropropane, HCl is generated by decomposition of the product at high temperature and high pressure, and the HCl may cause a certain damage to the conventionally used catalyst. The ionic liquid catalyst of the silica gel immobilized supported iron prepared by the preparation method disclosed by the invention has excellent thermal stability, can not be decomposed under the high-temperature and high-pressure reaction condition, and the ionic liquid immobilized on the surface can form a certain protection effect on the silica gel carrier, so that the damage of HCl to the catalyst is effectively reduced, and the catalytic efficiency of the catalyst is improved.
Compared with the prior art, the method for continuously preparing the 1, 3-pentachloropropane has the following advantages:
(1) The invention provides a method for continuously preparing 1, 3-pentachloropropane, using chloroethylene and carbon tetrachloride as raw materials, adopting a tubular fixed bed reactor to obtain 1, 3-pentachloropropane, the method can realize rapid, efficient and continuous reaction, save time and cost, has simple reaction equipment and can improve the operation efficiency.
(2) The invention provides a method for continuously preparing 1, 3-pentachloropropane, wherein the adopted silica gel immobilized iron-supported ionic liquid catalyst has excellent catalytic performance and thermal stability, can effectively improve the catalytic efficiency and the selectivity of the 1, 3-pentachloropropane.
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 were conventional reagents, which were purchased from conventional reagent manufacturing and selling companies, and the methods used, unless otherwise specified, were all prior art.
Example 1
The continuous preparation method of the 1, 3-pentachloropropane comprises the following steps:
preparing an ionic liquid catalyst of silica gel immobilized supported iron:
s1, 1-butyl-3-methylimidazole tetrafluoroborate ([ BMIM)]BF 4 ) And FeCl 2 Adding according to the mol ratio of 1:1, stirring at 90 ℃ under the protection of nitrogen for 48 h, and filtering out insoluble matters to obtain the iron-supported ionic liquid;
s2, adding tetraethoxysilane into a flask, stirring and heating to 55 ℃, then respectively adding the iron-supported ionic liquid obtained in the step S1 and absolute ethyl alcohol, uniformly mixing, dropwise adding a nitric acid solution with the mass concentration of 10%, standing and generating gel, and then aging at room temperature for 20 h; wherein the mass ratio of the added iron-supported ionic liquid to the added ethyl orthosilicate to the added absolute ethyl alcohol to the added nitric acid solution is 1:5:3:2;
and S3, vacuum drying the aged gel obtained in the step S2 at the temperature of 90 ℃ and the vacuum degree of-0.05 MPa for 10 h to obtain the silica gel immobilized supported iron ionic liquid catalyst.
(2) Continuous preparation of 1, 3-pentachloropropane:
in a tubular fixed bed reactor, the molar ratio of the addition amount of the chloroethylene to the carbon tetrachloride is 0.2:1, the reaction is carried out under the action of an ionic liquid catalyst of silica gel immobilized supported iron, the reaction temperature is 80 ℃, the reaction pressure is 0 MPa, and the mass airspeed is 0.5 h -1 Continuously preparing 1, 3-pentachloropropane.
Example 2
The continuous preparation method of the 1, 3-pentachloropropane comprises the following steps:
(1) Preparing an ionic liquid catalyst of silica gel immobilized supported iron:
s1, 3-methyl-1- (2-hydroxyethyl) imidazole chloride ([ HEMIM)]Cl) and FeCl 2 Added according to the mol ratio of 1:1, stirred under nitrogen at 110 ℃ for 48 h, and then filteredObtaining the ion liquid of the supported iron after insoluble matters;
s2, adding silica sol into a flask, stirring and heating to 65 ℃, then respectively adding the iron-supported ionic liquid obtained in the step S1 and absolute ethyl alcohol, uniformly mixing, dropwise adding a nitric acid solution with the mass concentration of 10%, standing and generating gel, and then aging at room temperature for 30 h; wherein the mass ratio of the added iron-supported ionic liquid to the silica sol to the absolute ethyl alcohol to the nitric acid solution is 1:15:10:8;
and S3, vacuum drying the aged gel obtained in the step S2 at the temperature of 110 ℃ and the vacuum degree of-0.05 MPa for 15 h to obtain the silica gel immobilized supported iron ionic liquid catalyst.
(2) Continuous preparation of 1, 3-pentachloropropane:
in a tubular fixed bed reactor, the molar ratio of the addition amount of the chloroethylene to the carbon tetrachloride is 1.5:1, the reaction is carried out under the action of an ionic liquid catalyst of silica gel immobilized supported iron, the reaction temperature is 150 ℃, the reaction pressure is 0.2 MPa, and the mass airspeed is 3 h -1 Continuously preparing 1, 3-pentachloropropane.
Example 3
The continuous preparation method of the 1, 3-pentachloropropane comprises the following steps:
(1) Preparing an ionic liquid catalyst of silica gel immobilized supported iron:
s1, 1-butyl-3-methylimidazole chloride ([ BMIM)]Cl) and FeCl 2 Adding according to the mol ratio of 1:1, stirring at 100 ℃ under the protection of nitrogen for 48 h, and filtering out insoluble matters to obtain the iron-supported ionic liquid;
s2, adding tetraethoxysilane into a flask, stirring and heating to 60 ℃, then respectively adding the iron-supported ionic liquid obtained in the step S1 and absolute ethyl alcohol, uniformly mixing, dropwise adding a nitric acid solution with the mass concentration of 10%, standing and generating gel, and then aging at room temperature for 24 h; wherein the mass ratio of the added iron-supported ionic liquid to the added ethyl orthosilicate to the added absolute ethyl alcohol to the added nitric acid solution is 1:6:7:3;
and S3, vacuum drying the aged gel obtained in the step S2 at the temperature of 100 ℃ and the vacuum degree of-0.05 MPa for 12 h to obtain the silica gel immobilized supported iron ionic liquid catalyst.
(2) Continuous preparation of 1, 3-pentachloropropane:
in a tubular fixed bed reactor, the molar ratio of the addition amount of the chloroethylene to the carbon tetrachloride is 0.6:1, the reaction is carried out under the action of an ionic liquid catalyst of silica gel immobilized supported iron, the reaction temperature is 110 ℃, the reaction pressure is 0.15 MPa, and the mass airspeed is 1.1 h -1 Continuously preparing 1, 3-pentachloropropane.
Example 4
The continuous preparation method of the 1, 3-pentachloropropane comprises the following steps:
(1) Preparing an ionic liquid catalyst of silica gel immobilized supported iron:
s1, 3-methyl-1- (2-hydroxyethyl) imidazole tetrafluoroborate ([ HEMIM)]BF 4 ) And FeCl 2 Adding according to the mol ratio of 1:1, stirring at 100 ℃ under the protection of nitrogen for 48 h, and filtering out insoluble matters to obtain the iron-supported ionic liquid;
s2, adding water glass into a flask, stirring and heating to 63 ℃, then respectively adding the iron-supported ionic liquid obtained in the step S1 and absolute ethyl alcohol, uniformly mixing, dropwise adding a nitric acid solution with the mass concentration of 10%, standing and generating gel, and then aging at room temperature for 26 h; wherein the mass ratio of the added iron-supported ionic liquid to the added water glass to the added absolute ethyl alcohol to the added nitric acid solution is 1:8:7:5;
and S3, vacuum drying the aged gel obtained in the step S2 at the temperature of 100 ℃ and the vacuum degree of-0.05 MPa for 12 h to obtain the silica gel immobilized supported iron ionic liquid catalyst.
(2) Continuous preparation of 1, 3-pentachloropropane:
in a tubular fixed bed reactor, the molar ratio of the addition amount of the chloroethylene to the carbon tetrachloride is 1.2:1, the reaction is carried out under the action of an ionic liquid catalyst of silica gel immobilized supported iron, the reaction temperature is 130 ℃, the reaction pressure is 0.11 MPa, and the quality is improvedWeight space velocity of 0.8 h -1 Continuously preparing 1, 3-pentachloropropane.
Comparative example 1
Comparative example 1 was different from example 3 in that 1-butyl-3-methylimidazole chloride ([ BMIM ] Cl) was replaced with 2-chloro-1, 3-dimethylimidazole chloride (CAS number: 37091-73-9) in the preparation step S1 of the silica gel-immobilized iron-supported ionic liquid catalyst, and other parameters and operations were the same as in example 3.
Comparative example 2 is different from example 3 in that the ethyl orthosilicate in the preparation step S2 of the silica gel-immobilized iron-supported ionic liquid catalyst was replaced with white carbon black, and other parameters and operations are the same as example 3.
Compared with example 3, the difference of comparative example 3 is that in the preparation step S2 of the silica gel immobilized iron-supported ionic liquid catalyst, the mass ratio of the added iron-supported ionic liquid, ethyl orthosilicate, absolute ethyl alcohol and nitric acid solution is 1:3:2:1, and other parameters and operations are the same as example 3.
The products obtained in the preparation methods of examples 1 to 4 and comparative examples 1 to 3 were subjected to gas chromatography detection analysis to obtain the conversion (%) of vinyl chloride and the selectivity (%) of 1, 3-pentachloropropane as shown in Table 1.
TABLE 1
| Group of | Conversion of vinyl chloride (%) | Selectivity (%) |
| Example 1 | 97.6 | 98.5 |
| Example 2 | 96.5 | 95.9 |
| Example 3 | 99.7 | 99.8 |
| Example 4 | 97.8 | 96.3 |
| Comparative example 1 | 91.6 | 92.3 |
| Comparative example 2 | 87.6 | 89.7 |
| Comparative example 3 | 83.1 | 84.1 |
As is clear from Table 1, the products obtained by the production methods of examples 1 to 4 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%. It can be seen that the ionic liquid catalyst of silica gel immobilized supported iron prepared by the embodiments 1-4 can effectively improve the selectivity of synthesized 1, 3-pentachloropropane.
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 process for the continuous preparation of 1, 3-pentachloropropane, comprising the steps of:
adopting a tubular fixed bed reactor, taking chloroethylene and carbon tetrachloride as raw materials, and carrying out reaction under the action of an ionic liquid catalyst of silica gel immobilized supported iron to continuously prepare 1, 3-pentachloropropane;
the preparation method of the silica gel immobilized supported iron ionic liquid catalyst comprises the following steps:
s1, mixing the ionic liquid and FeCl 2 Stirring under the protection of nitrogen, and filtering out insoluble matters to obtain iron-supported ionic liquid;
s2, adding a silicon source into the flask, stirring and heating to 55-65 ℃, then respectively adding the iron-supported ionic liquid obtained in the step S1 and absolute ethyl alcohol, uniformly mixing, dropwise adding a nitric acid solution with the mass concentration of 10%, standing and generating gel, and then aging for 20-30 hours at room temperature;
s3, carrying out vacuum drying on the aged gel obtained in the step S2 to obtain the silica gel immobilized supported iron ionic liquid catalyst;
the mass ratio of the iron-supported ionic liquid, the silicon source, the absolute ethyl alcohol and the nitric acid solution added in the reaction process of the step S2 is 1:5-15:3-10:2-8;
the ionic liquid in the step S1 is one of 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole tetrafluoroborate, 3-methyl-1- (2-hydroxyethyl) imidazole chloride and 3-methyl-1- (2-hydroxyethyl) imidazole tetrafluoroborate;
the silicon source in the step S2 is ethyl orthosilicate.
2. The process for continuous production of 1, 3-pentachloropropane according to claim 1, wherein in step S1, the ionic liquid is an ionic liquidAnd FeCl 2 Under the protection of nitrogen, 48 and h are stirred at the temperature of 90-110 ℃.
3. The method for continuously preparing 1, 3-pentachloropropane according to claim 1, wherein in step S1, the ionic liquid is mixed with FeCl 2 The molar ratio of (2) is 1:1.
4. The method for continuously preparing 1, 3-pentachloropropane according to claim 1, wherein the vacuum drying temperature in the step S3 is 90-110 ℃, the vacuum degree is-0.05 MPa, and the time is 10-15 hours.
5. A process for the continuous preparation of 1, 3-pentachloropropane according to claim 1, in the preparation process of the tubular fixed bed reactor, the molar ratio of the chloroethylene to the carbon tetrachloride is 0.2-1.5:1.
6. A process for the continuous preparation of 1, 3-pentachloropropane according to claim 1, the reaction temperature of the 1, 3-pentachloropropane in the preparation process of the tubular fixed bed reactor is 80-150 ℃, the reaction pressure is 0-0.2 MPa, and the mass airspeed is 0.5-3 h -1 。
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