CN110511112A - A kind of preparation method of 1,1,2,3- tetrachloropropylenes - Google Patents
A kind of preparation method of 1,1,2,3- tetrachloropropylenes Download PDFInfo
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- CN110511112A CN110511112A CN201910758215.2A CN201910758215A CN110511112A CN 110511112 A CN110511112 A CN 110511112A CN 201910758215 A CN201910758215 A CN 201910758215A CN 110511112 A CN110511112 A CN 110511112A
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- carbon tetrachloride
- tetrachloropropylene
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- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical class ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 168
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 52
- 239000000047 product Substances 0.000 claims abstract description 39
- 238000000197 pyrolysis Methods 0.000 claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 18
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 13
- UTACNSITJSJFHA-UHFFFAOYSA-N 1,1,1,3-tetrachloropropane Chemical compound ClCCC(Cl)(Cl)Cl UTACNSITJSJFHA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- -1 (1,10- phenanthroline) hexafluorophosphoric acid iron Chemical compound 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000004683 dihydrates Chemical class 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 37
- 238000004458 analytical method Methods 0.000 description 35
- 239000000203 mixture Substances 0.000 description 31
- 238000005070 sampling Methods 0.000 description 30
- 239000007789 gas Substances 0.000 description 25
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 description 24
- VZEWJVRACUZHQR-UHFFFAOYSA-N 1,1,1,5-tetrachloropentane Chemical compound ClCCCCC(Cl)(Cl)Cl VZEWJVRACUZHQR-UHFFFAOYSA-N 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000012752 auxiliary agent Substances 0.000 description 12
- VKEIPALYOJMDAC-UHFFFAOYSA-N 3,3,3-trichloroprop-1-ene Chemical compound ClC(Cl)(Cl)C=C VKEIPALYOJMDAC-UHFFFAOYSA-N 0.000 description 11
- LIPPKMMVZOHCIF-UHFFFAOYSA-N 1,1,2-trichloroprop-1-ene Chemical compound CC(Cl)=C(Cl)Cl LIPPKMMVZOHCIF-UHFFFAOYSA-N 0.000 description 10
- JFEVIPGMXQNRRF-UHFFFAOYSA-N 1,1,3-trichloroprop-1-ene Chemical compound ClCC=C(Cl)Cl JFEVIPGMXQNRRF-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 6
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229950011008 tetrachloroethylene Drugs 0.000 description 6
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 238000007033 dehydrochlorination reaction Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- ZXPCCXXSNUIVNK-UHFFFAOYSA-N 1,1,1,2,3-pentachloropropane Chemical compound ClCC(Cl)C(Cl)(Cl)Cl ZXPCCXXSNUIVNK-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- HIILBTHBHCLUER-IWQZZHSRSA-N (z)-1,2,3-trichloroprop-1-ene Chemical compound ClC\C(Cl)=C\Cl HIILBTHBHCLUER-IWQZZHSRSA-N 0.000 description 2
- FTCVHAQNWWBTIV-UHFFFAOYSA-N 1,1,1,2,2-pentachloropropane Chemical compound CC(Cl)(Cl)C(Cl)(Cl)Cl FTCVHAQNWWBTIV-UHFFFAOYSA-N 0.000 description 2
- IYFMQUDCYNWFTL-UHFFFAOYSA-N 1,1,2,2,3-pentachloropropane Chemical class ClCC(Cl)(Cl)C(Cl)Cl IYFMQUDCYNWFTL-UHFFFAOYSA-N 0.000 description 2
- UDPHJTAYHSSOQB-UHFFFAOYSA-N 1,2,2,3-tetrachloropropane Chemical class ClCC(Cl)(Cl)CCl UDPHJTAYHSSOQB-UHFFFAOYSA-N 0.000 description 2
- FALCMQXTWHPRIH-UHFFFAOYSA-N 2,3-dichloroprop-1-ene Chemical group ClCC(Cl)=C FALCMQXTWHPRIH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-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
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- ZDCWZRQSHBQRGN-UHFFFAOYSA-N 1,1,1,2,3-pentafluoropropane Chemical compound FCC(F)C(F)(F)F ZDCWZRQSHBQRGN-UHFFFAOYSA-N 0.000 description 1
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical class ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 description 1
- HIILBTHBHCLUER-UHFFFAOYSA-N 1,2,3-trichloroprop-1-ene Chemical class ClCC(Cl)=CCl HIILBTHBHCLUER-UHFFFAOYSA-N 0.000 description 1
- QJMGASHUZRHZBT-UHFFFAOYSA-N 2,3-dichloro-1,1,1-trifluoropropane Chemical compound FC(F)(F)C(Cl)CCl QJMGASHUZRHZBT-UHFFFAOYSA-N 0.000 description 1
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000005625 Tri-allate Substances 0.000 description 1
- MWBPRDONLNQCFV-UHFFFAOYSA-N Tri-allate Chemical compound CC(C)N(C(C)C)C(=O)SCC(Cl)=C(Cl)Cl MWBPRDONLNQCFV-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- 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
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of 1,1,2,3- tetrachloropropylene, comprising: (1) synergist containing neodymium is prepared, it is spare；(2) carbon tetrachloride mixed liquor is prepared, it is spare；(3) carbon tetrachloride mixed liquor and ethylene are continuously passed through in second reactor and are reacted, obtain reaction product；(4) by isolated first logistics of reaction product and the second logistics, third―party logistics and the 4th logistics will be obtained after the second logistics separation；(5) by the first logistics and third―party logistics rectifying, the carbon tetrachloride of 1,1,1,3- tetra- chloropropane and recycling is obtained；(6) 1,1,1,3- tetra- chloropropane is subjected to cracking reaction, obtains pyrolysis product after condensing and separating tail gas；(7) pyrolysis product is subjected to gas phase chlorination, obtains gas phase chlorination product after condensing and separating tail gas；(8) gas phase chlorination product is cracked, collecting reaction product and after condensing and separating tail gas obtains 1,1,2,3- tetrachloropropylene products.The present invention has simple process, high-efficient, at low cost, environmentally protective advantage.
Description
Technical field
The present invention relates to the preparation methods containing chloro-alkenes, belong to organic synthesis field, and in particular to a kind of 1,1,2,3- tetrachloros
The preparation method of propylene.
Background technique
1,1,2,3- tetrachloropropylene (TCP, also known as HCC-1230xa) is to prepare chemical herbicide wheat to fear the main of missible oil
One of intermediate and the primary raw material of Pesticidal products tri-allate.1,1,2,3- tetrachloropropylene can also be used to produce as raw material
CFC-1233xf, HFO-1234ze, HFC-245eb, HCFC-244bb, HFO-1234yf, 2,3- bis- chloro- 1,1,1 ,-trifluoropropyl
Alkane (HCFC-243db) etc., wherein HFO-1234yf is new generation of environment protection fluorinated refrigerant, typical feature be have it is lower
GWP value (its value is 4), the car air conditioner refrigerant for current large-scale use are a kind of potential, economical and direct
Alternative solution.The production method of HFO-1234yf mainly has using trifluoro propene as raw material, by raw material of hexafluoropropene and with 1,1,
2,3- tetrachloropropylenes are the production technology of raw material, and raw materials for production of 1,1,2, the 3- tetrachloropropylene as HFO-1234yf, production
Simple process, industrialized production easy to accomplish.Therefore, 1,1,2,3- tetrachloropropylene is as new generation of environment protection fluorinated refrigerant HFO-
The raw materials for production of 1234yf, preparation method become research hotspot.
As China Patent Publication No. CN101754941A provides the method for the chloro- 1- propylene of preparation 1,1,2,3- tetra-, including
In the gas phase, in the presence of the first catalyst, make CH2ClCCl2CH2Cl dehydrochlorination is to generate including CHCl=CClCH2Cl
The first intermediate product；Make the CHCl=CClCH of first intermediate product2At least part chlorination of Cl, with formed include
CHCl2CCl2CH2The second intermediate product of Cl；In the gas phase, in the presence of the second catalyst, make to produce among described second
The CHCl of object2CCl2CH2At least part dehydrochlorination of Cl includes CCl to be formed2=CClCH2The final product of Cl.Deficiency
Place is that raw material is not easy to obtain, catalyst can not recycle, is at high cost.
If China Patent Publication No. CN101955414A discloses a kind of 1,1,2,3- tetrachloropropylene production technology, including 1,
2,3- trichloropropanes dehydrochlorination in the presence of aqueous slkali, obtains 2,3- dichloropropylene；2,3- dichloropropylene chlorinations generate 1,
2,2,3- tetra- chloropropanes；1,2,2,3- tetra- chloropropane dehydrochlorination in the presence of aqueous slkali, obtains 1,2,3- tri chloropropenes；1,
2,3- tri chloropropene chlorinations generate 1,1,2,2,3- pentachloropropanes；Rectification and purification resulting 1,1,2,2,3- pentachloropropane；1,1,
2,2,3- pentachloropropanes dehydrochlorination in the presence of aqueous slkali obtains 1,1,2,3- tetrachloropropylene.Shortcoming be yield it is low,
Energy consumption is high, " three wastes " discharge amount is big.
It, should if China Patent Publication No. CN102911006A is related to a kind of method for preparing the low moisture content tetrachloropropylene of high-purity
After rectifying column rectifying, liquid alkaline and phase transfer catalyst (quaternary ammonium salt) is added in pentachloropropane by method thereto, and reaction obtains four
Chloropropene crude product controls water content in 80ppm hereinafter, then obtaining purity by rectifying column rectifying is 99.5% by dehydration
More than, water content is in the low moisture content tetrachloropropylene of 30ppm high-purity below.Shortcoming be catalyst can not recycle, " three wastes "
Discharge amount is big.
In conclusion currently preparing 1, the method for 1,2,3- tetrachloropropylene is although more, but there are raw materials to be not easy to obtain, yield
Low, such or such problem such as energy consumption is high, catalyst can not recycle, " three wastes " discharge amount is big.Therefore, develop a green,
Low cost, 1,1,2,3- tetrachloropropylene preparation method of low energy consumption meet needed for industry.
Summary of the invention
It is high-efficient in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of simple process, it is at low cost, it is green
The preparation method for 1,1,2, the 3- tetrachloropropylene that colour circle is protected, this method have great market application prospect.
The technical solution that the present invention uses to achieve the above object are as follows: a kind of preparation method of 1,1,2,3- tetrachloropropylenes,
The following steps are included:
(1) by weight, 100 parts of molecular sieve is added in the first reactor, adds water and stirs to obtain slurries, adds first
150-300 parts of alcohol solution, filtering, washing filter cake to neutrality is dried, then three (1,10- phenanthroline) hexafluoro phosphorus are added in roasting
It is sour iron 0.05-0.7 parts, 200-500 parts of acetone, 0.02-0.5 parts of (III) dihydrate of hexafluoro -2,4- acetylacetone,2,4-pentanedione neodymium, bis- (double
Trimethyl silicon substrate) 1-8 parts of amine zinc, 5-20 parts of alkyl imidazoline phosphate, 2-6h is reacted, is filtered, drying obtains synergy containing neodymium
Agent, it is spare；
(2) synergist containing neodymium, tributyl phosphate, the iron powder obtained step (1) is added in carbon tetrachloride, stirs evenly
To carbon tetrachloride mixed liquor, the content of the synergist containing neodymium is 0.5-2.5wt% (wt%, quality in the carbon tetrachloride mixed liquor
Percentage composition), the content of tributyl phosphate is 0.5-1.0wt%, and the content of iron powder is 0.5-1.0wt%, spare；
(3) the carbon tetrachloride mixed liquor that step (2) obtains continuously is passed through in second reactor with ethylene and is reacted, institute
The temperature for stating reaction is 90-120 DEG C, residence time 1-2h, system pressure 0.5-1.0Mpa, carbon tetrachloride and ethylene molar
Than obtaining the first reaction product for 1-4:1；
(4) the first reaction product that step (3) obtains is passed through in the first membrane separator, obtained after separation the first logistics and
Second logistics, the second logistics is passed through in the second membrane separator, and third―party logistics and the 4th logistics are obtained after separation；
(5) the first logistics and third―party logistics obtained step (4) carries out rectifying, obtains 1,1,1,3- tetra- chloropropane
(HCC-250fb) and recycling carbon tetrachloride；
(6) 1,1,1,3- tetra- chloropropane for obtaining step (5) carries out cracking reaction, and the temperature of the cracking reaction is
350-500 DEG C, residence time 1-8s, pyrolysis product is obtained after condensing and separating tail gas；
(7) pyrolysis product for obtaining step (6) carries out gas phase chlorination, and the temperature of the gas phase chlorination is 140-170 DEG C,
Residence time is 0.5-5.5s, and the molar ratio of chlorine and pyrolysis product is 1-4:1, obtains gas phase chlorination after condensing and separating tail gas
Product；
(8) the gas phase chlorination product that step (7) obtains is cracked, the temperature of the cracking is 350-500 DEG C, is stopped
Time is 2-15s, and collecting reaction product condensation, rectifying obtain 1,1,2,3- tetrachloropropylene products.
As the preferred embodiment of the present invention, the mass concentration of methanol aqueous solution described in step (1) is 20-
40%.
As the preferred embodiment of the present invention, the temperature of roasting described in step (1) is 400-600 DEG C, and the time is
2-6h。
As the preferred embodiment of the present invention, molecular sieve described in step (1) is ZSM-5 molecular sieve.
As the preferred embodiment of the present invention, iron powder described in step (2) is 80-200 mesh.
As the preferred embodiment of the present invention, the first membrane separator operating pressure described in step (4) is 0.5-
1.0Mpa, operation temperature are 15-40 DEG C, and the second membrane separator operating pressure is 1.0-1.5Mpa, and operation temperature is 25-60 DEG C.
As the preferred embodiment of the present invention, the 4th logistics that step (4) obtain can be subjected to rectifying, to recycle wherein
Synergist containing neodymium.
As the preferred embodiment of the present invention, the temperature of rectifying described in step (5) is 120-160 DEG C, reflux ratio
For 2-6.
As the preferred embodiment of the present invention, the carbon tetrachloride of recycling described in step (5) can be returned to step
(2) it is recycled in.
As the preferred embodiment of the present invention, the residence time described in step (7) is 0.5-1s.
During step (3) liquid phase continuous catalysis telomerisation, ethylene, carbon tetrachloride pass through respectively mass flowmenter,
Constant flow pump controls flow.The reaction can be implemented in the reactor of the teflon lined equipped with blender, insertion tube of going to the bottom.
Carbon tetrachloride and ethylene gas are continuously passed through in reactor by pass gaseous diffuser according to required molar ratio, and reaction solution is thick
Product are drawn by the bottom insertion tube with filter cloth, continuously successively introduce two-stage difference film point by constant flow pump with certain flow velocity
From being separated in device.
In step (3) liquid phase continuous catalysis telomerisation, it is catalyst, preferably iron that iron powder, iron filings or iron wire, which can be used,
Powder, the iron particle size are slurried less than 200 mesh, preferably 80-200 mesh so as to mix with carbon tetrachloride, continuously enter reaction
Device.In step (3) liquid phase continuous catalysis telomerisation, using tributyl phosphate as auxiliary agent.Synergist containing neodymium, tricresyl phosphate fourth
Before ester, iron powder reaction start and carbon tetrachloride is configured to mixed liquor according to a certain percentage, then quantitative together to be continuously passed through instead
It answers in device.
In step (3) liquid phase continuous catalysis telomerisation, HCC-250fb crude product is passed through into constant flow pump from filter first
The bottom insertion tube of cloth is led in the first membrane separator with certain flow rate, operating pressure 0.5-1.0Mpa, operation temperature 15-40
DEG C, introduce flow 10-70ml/min, preferably 40ml/min.Crude product is separated into the non-pole such as carbon tetrachloride after the first membrane separator
Property object (logistics 1) and HCC-250fb/ auxiliary agent/catalyst mixture (logistics 2) two streams.Wherein, logistics 1 forms (quality hundred
Divide content) are as follows: 85-90% carbon tetrachloride, 5-10%HCC-250fb, 2-3% tetrachloro-ethylene, 0.5-1% carbon trichloride.Logistics 2
It forms (mass percentage) are as follows: 85-93%HCC-250fb, catalyst 1-3%, the 2.3-5% of synergist containing neodymium, 1-6% tetrachloro
Change carbon, 1-3% carbon trichloride, 1,1,1,5- tetra- chloropentane 0.5-1.2%.
Logistics 2 is flowed into the second membrane separator by pump with certain flow velocity, operating pressure 1.0-1.5Mpa, operation temperature
25-60 DEG C, flow 10-40ml/min, preferably 20ml/min.Be separated into the mixtures such as HCC-250fb (logistics 3) and catalyst/
Synergist containing neodymium etc. mixtures (logistics 4) two streams.Wherein, logistics 3 forms (mass percentage) are as follows: 86-95%HCC-
250fb, 1-15% carbon tetrachloride, 1-4% carbon trichloride.Logistics 4 forms (mass percentage) are as follows: 5-10%HCC-250fb,
1-5% carbon tetrachloride, 2-3% carbon trichloride, 1,1,1,5- tetra- chloropentane 1-5%, catalyst 11-20%, the 70- of synergist containing neodymium
84%.To avoid some such as 1,1,1,5- tetra- chloropentanes of heavy by-product etc. from accumulating, logistics 4 can be subjected to continuously or periodically portion
It distinguishes and removes.The material cleared out of can carry out batch fractionating, to recycle useful object therein.Logistics 1 mixed with logistics 3 after together into
Enter rectifying column to be separated.
Logistics 1 and logistics 3 are mixed into rectifying column and carry out rectification under vacuum (preferably 30-200mmHg), light group isolated
(predominantly carbon tetrachloride) is divided to can return to step (2) for preparing carbon tetrachloride mixed liquor, mainly containing the intermediate of HCC-250fb
Logistics can be directly used for step (6) reaction.
In step (6) reaction process, mainly the intermediate containing HCC-250fb is by pump directly with certain flow rate (20-
It 40ml/min) imports shell and tube reactor and carries out Pintsch process.350-500 DEG C of cracking temperature, normal pressure, residence time 1-8s is split
1 after solution, 1,3- tri chloropropene/3,3,3- tri chloropropene, after condensing and separating tail gas, obtain pyrolysis product, pyrolysis product without
Purification & isolation is needed, can be directly used for step (7) reaction.
In step (7) reaction process, pyrolysis product directly imports shell and tube reactor with certain flow rate and carries out gas phase chlorine
Change.140-170 DEG C of chlorination temperature, normal pressure, residence time 0.5-5.5s, chlorine and pyrolysis product molar ratio 1-4:1, chlorine with split
It solves product molar ratio and exceeds 1.2:1, then 1,1,1,2,3- pentachloropropane selectively reduces obvious.Contain 1,1,1,2,3- after chlorination
The mixture of pentachloropropane is condensed and separated HCl tail gas (a small amount of chlorine for retaining remaining), obtains chlorizate, chlorizate
Without purification & isolation, step (8) reaction can be directly used for.
In step (8) reaction process, chlorizate directly imports shell and tube reactor with certain flow rate and carries out high anneal crack
Solution.350-500 DEG C of cracking temperature, normal pressure, residence time 2-15s, 1 after cracking, 1,2,3- tetrachloropropylene mixture, through condensing
After separating HCl tail gas, 1,1,2,3- tetrachloropropylenes are obtained, 1,1,2,3- tetrachloropropylene is obtained by rectifying column rectifying by dehydration
Product.
To all shell and tube reactors and catalytic reactor material, there is no limit any acid corrosion-resistant material is equal in the present invention
It can be used for the present invention, preferably Hastelloy, Inconel etc. commonly uses corrosion-resistant material.After HCl, tail gas and separation in the present invention
HF, Cl2It can be further recycled by compressor.
Compared with prior art, advantages of the present invention are as follows:
1, at low cost, HCC-250fb crude product through two-stage UF membrane, catalyst and synergist containing neodymium can realize recovery and
Separation costs are cheap, greatly reduce production cost；
2, simple process, step (6)-(8) reaction are gas phase successive reaction, and intermediate reduces separation without purifying
The use of equipment；
3, environmentally protective, greatly simplify the preparation process of 1,1,2,3- tetrachloropropylene, reduces equipment, energy makes
With reducing the discharge of " three wastes ".
4, high-efficient, synergist containing neodymium significantly improves the efficiency of catalyst telomerization reaction, conversion of ethylene 99% or more,
HCC-250fb selectivity is 98% or more.
Specific embodiment
Invention is further described in detail by the following examples, but the present invention is not limited in these following implementations
Example.
Embodiment 1
(1) synergist containing neodymium is prepared
By weight, it with the ZSM-5 molecular sieve that 100 parts are added in stirred reactor, adds water and stirs to obtain slurries, dropwise
200 parts of methanol that mass concentration is 30%, filtering are added, washing filter cake to neutrality is dried, and 500 DEG C of roasting 4h are put into flask
In, it adds 0.1 part of hexafluorophosphoric acid iron of three (1,10- phenanthroline), 300 parts of acetone, hexafluoro -2,4- acetylacetone,2,4-pentanedione neodymium (III) two
0.07 part of hydrate, 5 parts of amine zinc of bis- (double trimethyl silicon substrates), are stirred to react 4h by 11 parts of alkyl imidazoline phosphate, through filtering,
Drying, is made synergist containing neodymium, spare.
(2) carbon tetrachloride mixed liquor is prepared
Carbon tetrachloride is added in synergist containing neodymium, auxiliary agent tributyl phosphate, the 200 mesh iron powder of catalyst that step (1) is obtained
In, it is uniformly mixing to obtain carbon tetrachloride mixed liquor, the content of the synergist containing neodymium is 0.5wt%, phosphoric acid in carbon tetrachloride mixed liquor
The content of tributyl is 1.0wt%, and the content of iron powder is 1.0wt%, spare.
(3) kettle nitrogen replacement will be reacted twice, and will then raise temperature to 90 DEG C, and be 1 according to carbon tetrachloride and ethylene molar ratio, stop
The requirement of time 120min is stayed, is respectively continuously passed through carbon tetrachloride mixed liquor and ethylene two streams in reaction kettle simultaneously, and
Respective flow is controlled by constant flow pump and mass flowmenter.At the same time, the discharging mouth containing continuous constant speed of HCC-250fb reaction solution is drawn
Stream, maintenance system pressure 1.0Mpa, continuous sampling analysis.It can be observed to calculate on the basis of ethylene, conversion ratio 99.1%, HCC-
250fb selectivity 98.5%.
(4) reaction solution containing HCC-250fb is continuously conveyed with the flow of 70ml/min to the first UF membrane by constant flow pump
In device, the first membrane separator membrane area 0.4m2, operating pressure 0.5Mpa, 40 DEG C of operation temperature.After separation, HCC-250fb is anti-
Liquid is answered to be divided into the non-polar materials such as carbon tetrachloride (logistics 1) and HCC-250fb/ auxiliary agent/two strands of objects of catalyst mixture (logistics 2)
Stream.By sampling analysis, logistics 1 can be observed and form (mass percentage) are as follows: 87% carbon tetrachloride, 10%HCC-250fb,
2.0% tetrachloro-ethylene, 1.0% carbon trichloride.Logistics 2 forms (mass percentage) are as follows: 90%HCC-250fb, catalyst
1%, synergist containing neodymium 2.5%, carbon tetrachloride 4.5%, 1.2% carbon trichloride, 1,1,1,5- tetra- chloropentane 0.8%.Logistics 2 is logical
It crosses pump to be continuously conveyed with 10ml/min flow velocity into the second membrane separator, the second membrane separator membrane area 0.4m2, operating pressure
1.5Mpa, 50 DEG C of operation temperature.Logistics 2 is divided into the mixtures such as HCC-250fb (logistics 3) and catalyst/synergist containing neodymium etc.
Mixture (logistics 4) two streams.By sampling analysis, logistics 3 can be observed and form (mass percentage) are as follows: 86%HCC-
250fb, 10% carbon tetrachloride, 2% carbon trichloride, other 2.0%.Logistics 4 forms (mass percentage) are as follows: 5%HCC-
250fb, 5% carbon tetrachloride, 2% carbon trichloride, 1%1,1,1,5- tetra- chloropentanes, catalyst 15%, synergist containing neodymium 72%.
Logistics 4 can be continued cycling through and be applied, and to avoid some such as 1,1,1,5- tetra- chloropentanes of heavy by-product etc. from accumulating, logistics 4 is carried out continuously
Or periodically part is removed.The material cleared out of can carry out batch fractionating, further to recycle useful object therein.
(5) logistics 1 and 3 mixed liquor of logistics are delivered in rectifying knockout tower, which is provided with the condenser of cooling water,
3L round-bottomed flask reboiler, packed height 1m, using oil bath heating, reflux ratio uses 2, and reboiler temperature rises to 158 by 124 DEG C
DEG C terminate.Overhead light (predominantly carbon tetrachloride) is recycled to step (2) reuse, and tower bottom is the intermediate containing HCC-250fb,
By sampling analysis intermediate, it is 98wt% that 1,1,1,3- tetra- chloropropane (HCC-250fb) content, which can be observed,.
(6) shell and tube reactor 1 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 8mm, long 35cm, single tube totally 20).Temperature rise in shell and tube reactor is then passed through into meter to 350 DEG C in advance
Intermediate containing HCC-250fb is passed through shell and tube reactor 1, residence time 1s, mixture warp with the flow velocity of 1g/min by amount pump
HCl tail gas is removed in condensation, obtains pyrolysis product.By sampling analysis, HCC-250fb conversion ratio 90.0%, tri chloropropene (1,
1,3- tri chloropropene/3,3,3- tri chloropropene) selectivity 99%.
(7) shell and tube reactor 2 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 6mm, long 50cm, single tube totally 40.Temperature rise in shell and tube reactor is then passed through into metering to 140 DEG C in advance
Pump is 1.0 according to chlorine and pyrolysis product (1.5g/min) molar ratio, the requirement of residence time 5.5s, under normal pressure, while by chlorine
Gas and pyrolysis product are delivered in shell and tube reactor 2.Reaction product is collected through condensation, obtains chlorizate.Sampled analysis,
99.7%, 1,1,1,2,3- pentachloro- third of tri chloropropene (1,1,3- tri chloropropene/3,3,3- tri chloropropene) conversion ratio can be observed
Alkane (HCC-240db) selectivity 99.00%.
(8) shell and tube reactor 3 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 5mm, long 45cm, single tube totally 30.Temperature rise in shell and tube reactor is then passed through into metering to 350 DEG C in advance
Chlorizate normal pressure is passed through by pump with the flow velocity of 1.5g/min, and residence time 15s, mixture is condensed, and removes HCl tail gas, warp
1,1,2,3- tetrachloropropylene (TCP) is obtained by rectifying column rectifying after water removal, by sampling analysis, conversion ratio, which can be observed, is
71%, 97.6% (being calculated on the basis of HCC-240db) of selectivity.
Embodiment 2
(1) synergist containing neodymium is prepared
By weight, it with the ZSM-5 molecular sieve that 100 parts are added in stirred reactor, adds water and stirs to obtain slurries, dropwise
300 parts of methanol that mass concentration is 20%, filtering are added, washing filter cake to neutrality is dried, and 600 DEG C of roasting 2h are put into flask
In, it adds 0.05 part of hexafluorophosphoric acid iron of three (1,10- phenanthroline), 200 parts of acetone, hexafluoro -2,4- acetylacetone,2,4-pentanedione neodymium (III) two
0.02 part of hydrate, 1 part of amine zinc of bis- (double trimethyl silicon substrates) 5 parts of alkyl imidazoline phosphate, are stirred to react 2h, are filtered, and dry
It is dry, synergist containing neodymium is made, it is spare.
(2) carbon tetrachloride mixed liquor is prepared
Carbon tetrachloride is added in synergist containing neodymium, auxiliary agent tributyl phosphate, the 120 mesh iron powder of catalyst that step (1) is obtained
In, it is uniformly mixing to obtain carbon tetrachloride mixed liquor, the content of the synergist containing neodymium is 1.0wt%, phosphoric acid in carbon tetrachloride mixed liquor
The content of tributyl is 0.75wt%, and the content of iron powder is 0.8wt%, spare.
(3) kettle nitrogen replacement will be reacted twice, and will then raise temperature to 110 DEG C, and be 2 according to carbon tetrachloride and ethylene molar ratio,
Carbon tetrachloride mixed liquor and ethylene two streams are passed through in reaction kettle simultaneously respectively, and pass through by the requirement of residence time 90min
Constant flow pump and mass flowmenter control respective flow.At the same time, the continuous constant speed drainage of discharging mouth containing HCC-250fb reaction solution,
Maintenance system pressure 0.7Mpa, continuous sampling analysis.It can be observed to calculate on the basis of ethylene, conversion ratio 99%, HCC-250fb
Selectivity 98.0%.
(4) reaction solution containing HCC-250fb is continuously conveyed with the flow of 40ml/min to the first UF membrane by constant flow pump
In device, the first membrane separator membrane area 0.4m2, operating pressure 0.8Mpa, 25 DEG C of operation temperature.After separation, HCC-250fb is anti-
Liquid is answered to be divided into the non-polar materials such as carbon tetrachloride (logistics 1) and HCC-250fb/ auxiliary agent/two strands of objects of catalyst mixture (logistics 2)
Stream.By sampling analysis, logistics 1 can be observed and form (mass percentage) are as follows: 88% carbon tetrachloride, 9%HCC-250fb,
2.5% tetrachloro-ethylene, 0.5% carbon trichloride.Logistics 2 forms (mass percentage) are as follows: 90.5%HCC-250fb, catalyst
1%, synergist containing neodymium 3%, 4.0% carbon tetrachloride, 1.0% carbon trichloride, 1,1,1,5- tetra- chloropentane 0.5%.Logistics 2 passes through
Pump is continuously conveyed with 25ml/min flow velocity into the second membrane separator, the second membrane separator membrane area 0.2m2, operating pressure
1.2Mpa, 40 DEG C of operation temperature, logistics 2 is divided into the mixtures such as HCC-250fb (logistics 3) and catalyst/synergist containing neodymium etc.
Mixture (logistics 4) two streams.By sampling analysis, logistics 3 can be observed and form (mass percentage) are as follows: 89%HCC-
250fb, 7% carbon tetrachloride, 2% carbon trichloride, other 2%.Logistics 4 forms (mass percentage) are as follows: 6%HCC-250fb,
3% carbon tetrachloride, 2% carbon trichloride, 1,1,1,5- tetra- chloropentane 2%, catalyst quality 14%, the quality of synergist containing neodymium
73%.Logistics 4 can be continued cycling through and be applied, and to avoid some such as 1,1,1,5- tetra- chloropentanes of heavy by-product etc. from accumulating, logistics 4 is carried out
Continuously or periodically part is removed.The material cleared out of can carry out batch fractionating, further to recycle useful object therein.
(5) logistics 1 and 3 mixed liquor of logistics are delivered in rectifying knockout tower, which is provided with the condenser of cooling water,
3L round-bottomed flask reboiler, packed height 1m, using oil bath heating, reflux ratio uses 4, and reboiler temperature rises to 158 by 124 DEG C
DEG C terminate.Overhead light (predominantly carbon tetrachloride) is recycled to step (2) reuse, and tower bottom is the intermediate containing HCC-250fb,
By sampling analysis intermediate, it is 98.5wt% that 1,1,1,3- tetra- chloropropane (HCC-250fb) content, which can be observed,.
(6) shell and tube reactor 1 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 8mm, long 35cm, single tube totally 20.Temperature rise in shell and tube reactor is then passed through into metering to 450 DEG C in advance
Intermediate containing HCC-250fb is passed through shell and tube reactor 1 with the flow velocity of 1g/min by pump, and residence time 2s, mixture is through cold
It is solidifying, HCl tail gas is removed, pyrolysis product is obtained.By sampling analysis, HCC-250fb conversion ratio 96%, tri chloropropene can be observed
(1,1,3- tri chloropropene/3,3,3- tri chloropropene) selectivity 99.1%.
(7) shell and tube reactor 2 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 6mm, long 50cm, single tube totally 40.Temperature rise in shell and tube reactor is then passed through into metering to 140 DEG C in advance
Pump is 4.0 according to chlorine and pyrolysis product (1.5g/min) molar ratio, the requirement of residence time 3s, under normal pressure, while by chlorine
It is delivered in shell and tube reactor 2 with pyrolysis product.Reaction product is collected through condensation, obtains chlorizate.Sampled analysis, can
Observe 99.8%, 1,1,1,2,3- pentachloropropane of tri chloropropene (1,1,3- tri chloropropene/3,3,3- tri chloropropene) conversion ratio
(HCC-240db) selectivity 94.00%.
(8) shell and tube reactor 3 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 5mm, long 45cm, single tube totally 30.Temperature rise in shell and tube reactor is then passed through into metering to 400 DEG C in advance
Chlorizate normal pressure is passed through by pump with the flow velocity of 1.5g/min, and residence time 10s, mixture is condensed, and removes HCl tail gas, warp
1,1,2,3- tetrachloropropylene (TCP) is obtained by rectifying column rectifying after water removal, by sampling analysis, conversion ratio, which can be observed, is
74%, 98.4% (being calculated on the basis of HCC-240db) of selectivity.
Embodiment 3
(1) synergist containing neodymium is prepared
By weight, it with the ZSM-5 molecular sieve that 100 parts are added in stirred reactor, adds water and stirs to obtain slurries, dropwise
150 parts of methanol that mass concentration is 40%, filtering are added, washing filter cake to neutrality is dried, and 450 DEG C of roasting 6h are put into flask
In, it adds 0.7 part of hexafluorophosphoric acid iron of three (1,10- phenanthroline), 500 parts of acetone, hexafluoro -2,4- acetylacetone,2,4-pentanedione neodymium (III) two
0.5 part of hydrate, 3 parts of amine zinc of bis- (double trimethyl silicon substrates) 20 parts of alkyl imidazoline phosphate, are stirred to react 6h, are filtered, and dry
It is dry, synergist containing neodymium is made, it is spare.
(2) carbon tetrachloride mixed liquor is prepared
Carbon tetrachloride is added in synergist containing neodymium, auxiliary agent tributyl phosphate, the 100 mesh iron powder of catalyst that step (1) is obtained
In, it is uniformly mixing to obtain carbon tetrachloride mixed liquor, the content of the synergist containing neodymium is 1.5wt%, phosphoric acid in carbon tetrachloride mixed liquor
The content of tributyl is 0.5wt%, and the content of iron powder is 0.5wt%, spare.
(3) kettle nitrogen replacement will be reacted twice, and will then raise temperature to 120 DEG C, and be 4 according to carbon tetrachloride and ethylene molar ratio,
Carbon tetrachloride mixed liquor and ethylene two streams are passed through in reaction kettle simultaneously respectively, and pass through by the requirement of residence time 60min
Constant flow pump and mass flowmenter control respective flow.At the same time, the continuous constant speed drainage of discharging mouth containing HCC-250fb reaction solution,
Maintenance system pressure 0.5Mpa, continuous sampling analysis.It can be observed to calculate on the basis of ethylene, conversion ratio 99.2%, HCC-
250fb selectivity 98.8%.
(4) reaction solution containing HCC-250fb is continuously conveyed with the flow of 10ml/min to the first UF membrane by constant flow pump
In device, the first membrane separator membrane area 0.4m2, operating pressure 1.0Mpa, 15 DEG C of operation temperature.After separation, HCC-250fb is anti-
Liquid is answered to be divided into the non-polar materials such as carbon tetrachloride (logistics 1) and HCC-250fb/ auxiliary agent/two strands of objects of catalyst mixture (logistics 2)
Stream.By sampling analysis, logistics 1 can be observed and form (mass percentage) are as follows: 89% carbon tetrachloride, 8%HCC-250fb,
2.5% tetrachloro-ethylene, 0.5% carbon trichloride.Logistics 2 forms (mass percentage) are as follows: 88%HCC-250fb, catalyst
2%, synergist containing neodymium 3.0%, 5% carbon tetrachloride, 1.2% carbon trichloride, 1,1,1,5- tetra- chloropentane 0.8%.Logistics 2 passes through
Pump is continuously conveyed with 40ml/min flow velocity into the second membrane separator, the second membrane separator membrane area 0.2m2, operating pressure
1.2Mpa, 60 DEG C of operation temperature, logistics 2 is divided into the mixtures such as HCC-250fb (logistics 3) and catalyst/synergist containing neodymium etc.
Mixture (logistics 4) two streams.By sampling analysis, logistics 3 can be observed and form (mass percentage) are as follows: 90%HCC-
250fb, 5% carbon tetrachloride, 2% carbon trichloride, other 3.0%.Logistics 4 forms (mass percentage) are as follows: 6%HCC-
250fb, 2% carbon tetrachloride, 1.5% carbon trichloride, 1,1,1,5- tetra- chloropentane 1.5%, catalyst quality 11%, synergy containing neodymium
Agent quality 78%.Logistics 4 can be continued cycling through and be applied, to avoid some such as 1,1,1,5- tetra- chloropentanes of heavy by-product etc. from accumulating, object
Stream 4 carries out continuously or periodically part and removes.The material cleared out of can carry out batch fractionating, therein have further to recycle
Use object.
(5) logistics 1 and 3 mixed liquor of logistics are delivered in rectifying knockout tower, which is provided with the condenser of cooling water,
3L round-bottomed flask reboiler, packed height 1m, using oil bath heating, reflux ratio uses 6, and reboiler temperature rises to 158 by 124 DEG C
DEG C terminate.Overhead light (predominantly carbon tetrachloride) is recycled to step (2) reuse, and tower bottom is the intermediate containing HCC-250fb,
By sampling analysis intermediate, it is 98.7wt% that 1,1,1,3- tetra- chloropropane (HCC-250fb) content, which can be observed,.
(6) shell and tube reactor 1 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 8mm, long 35cm, single tube totally 20.Temperature rise in shell and tube reactor is then passed through into metering to 500 DEG C in advance
Intermediate containing HCC-250fb is passed through shell and tube reactor 1 with the flow velocity of 1g/min by pump, and residence time 5s, mixture is through cold
It is solidifying, HCl tail gas is removed, pyrolysis product is obtained.By sampling analysis, HCC-250fb conversion ratio 98%, tri chloropropene can be observed
(1,1,3- tri chloropropene/3,3,3- tri chloropropene) selectivity 97%.
(7) shell and tube reactor 2 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 6mm, long 50cm, single tube totally 40.Temperature rise in shell and tube reactor is then passed through into metering to 160 DEG C in advance
Pump is 2.0 according to chlorine and pyrolysis product (1.5g/min) molar ratio, the requirement of residence time 1s, under normal pressure, while by chlorine
It is delivered in shell and tube reactor 2 with pyrolysis product.Reaction product is collected through condensation, obtains chlorizate.Sampled analysis, can
Observe 99.1%, 1,1,1,2,3- pentachloropropane of tri chloropropene (1,1,3- tri chloropropene/3,3,3- tri chloropropene) conversion ratio
(HCC-240db) selectivity 98.00%.
(8) shell and tube reactor 3 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 5mm, long 45cm, single tube totally 30.Temperature rise in shell and tube reactor is then passed through into metering to 500 DEG C in advance
Chlorizate normal pressure is passed through by pump with the flow velocity of 1.5g/min, and residence time 2s, mixture is condensed, and HCl tail gas is removed, through removing
1,1,2,3- tetrachloropropylene (TCP) is obtained by rectifying column rectifying after water, by sampling analysis, conversion ratio, which can be observed, is
76%, 97.1% (being calculated on the basis of HCC-240db) of selectivity.
Embodiment 4
(1) synergist containing neodymium is prepared
By weight, it with the ZSM-5 molecular sieve that 100 parts are added in stirred reactor, adds water and stirs to obtain slurries, dropwise
220 parts of methanol that mass concentration is 20%, filtering are added, washing filter cake to neutrality is dried, and 550 DEG C of roasting 5h are put into flask
In, it adds 0.05 part of hexafluorophosphoric acid iron of three (1,10- phenanthroline), 400 parts of acetone, hexafluoro -2,4- acetylacetone,2,4-pentanedione neodymium (III) two
0.02 part of hydrate, 8 parts of amine zinc of bis- (double trimethyl silicon substrates), are stirred to react 4h by 11 parts of alkyl imidazoline phosphate, through filtering,
Drying, is made synergist containing neodymium, spare.
(2) carbon tetrachloride mixed liquor is prepared
Carbon tetrachloride is added in synergist containing neodymium, auxiliary agent tributyl phosphate, the 80 mesh iron powder of catalyst that step (1) is obtained
In, it is uniformly mixing to obtain carbon tetrachloride mixed liquor, the content of the synergist containing neodymium is 2.0wt%, phosphoric acid in carbon tetrachloride mixed liquor
The content of tributyl is 1.0wt%, and the content of iron powder is 0.8wt%, spare.
(3) kettle nitrogen replacement will be reacted twice, and will then raise temperature to 110 DEG C, and be 3 according to carbon tetrachloride and ethylene molar ratio,
Carbon tetrachloride mixed liquor and ethylene two streams are passed through in reaction kettle simultaneously respectively, and pass through by the requirement of residence time 90min
Constant flow pump and mass flowmenter control respective flow.At the same time, the continuous constant speed drainage of discharging mouth containing HCC-250fb reaction solution,
Maintenance system pressure 0.7Mpa, continuous sampling analysis.It can be observed to calculate on the basis of ethylene, conversion ratio 100%, HCC-
250fb selectivity 98.1%.
(4) reaction solution containing HCC-250fb is continuously conveyed with the flow of 40ml/min to the first UF membrane by constant flow pump
In device, the first membrane separator membrane area 0.4m2, operating pressure 0.8Mpa, 25 DEG C of operation temperature.After separation, HCC-250fb is anti-
Liquid is answered to be divided into the non-polar materials such as carbon tetrachloride (logistics 1) and HCC-250fb/ auxiliary agent/two strands of objects of catalyst mixture (logistics 2)
Stream.By sampling analysis, logistics 1 can be observed and form (mass percentage) are as follows: 90% carbon tetrachloride, 6%HCC-250fb,
3% tetrachloro-ethylene, 1% carbon trichloride.Logistics 2 forms (mass percentage) are as follows: 93%HCC-250fb, catalyst 1% contain
Neodymium synergist 2.5%, 1.5% carbon tetrachloride, 1.2% carbon trichloride, 1,1,1,5- tetra- chloropentane 0.8%.Logistics 2 by pump with
20ml/min flow velocity is continuously conveyed into the second membrane separator, the second membrane separator membrane area 0.2m2, operating pressure 1.0Mpa,
25 DEG C of operation temperature, logistics 2 is divided into the mixtures such as the mixtures such as HCC-250fb (logistics 3) and catalyst/synergist containing neodymium
(logistics 4) two streams.By sampling analysis, logistics 3 can be observed and form (mass percentage) are as follows: 95%HCC-250fb,
2% carbon tetrachloride, 1.5% carbon trichloride, other 1.5%.Logistics 4 forms (mass percentage) are as follows: 5%HCC-250fb,
3% carbon tetrachloride, 2% carbon trichloride, 1,1,1,5- tetra- chloropentane 1%, catalyst quality 18%, the quality of synergist containing neodymium
71%.Logistics 4 can be continued cycling through and be applied, and to avoid some such as 1,1,1,5- tetra- chloropentanes of heavy by-product etc. from accumulating, logistics 4 is carried out
Continuously or periodically part is removed.The material cleared out of can carry out batch fractionating, further to recycle useful object therein.
(5) logistics 1 and 3 mixed liquor of logistics are delivered in rectifying knockout tower, which is provided with the condenser of cooling water,
3L round-bottomed flask reboiler, packed height 1.5m, using oil bath heating, reflux ratio uses 2, and reboiler temperature is risen to by 124 DEG C
158 DEG C of end.Overhead light (predominantly carbon tetrachloride) is recycled to step (2) reuse, and tower bottom is the centre containing HCC-250fb
Body, by sampling analysis intermediate, it is 99wt% that 1,1,1,3- tetra- chloropropane (HCC-250fb) content, which can be observed,.
(6) shell and tube reactor 1 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 8mm, long 35cm, single tube totally 20.Temperature rise in shell and tube reactor is then passed through into metering to 450 DEG C in advance
Intermediate containing HCC-250fb is passed through shell and tube reactor 1 with the flow velocity of 1g/min by pump, and residence time 8s, mixture is through cold
It is solidifying, HCl tail gas is removed, pyrolysis product is obtained.By sampling analysis, HCC-250fb conversion ratio 99%, tri chloropropene can be observed
(1,1,3- tri chloropropene/3,3,3- tri chloropropene) selectivity 96%.
(7) shell and tube reactor 2 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 6mm, long 50cm, single tube totally 40.Temperature rise in shell and tube reactor is then passed through into metering to 170 DEG C in advance
Pump is 3.0 according to chlorine and pyrolysis product (1.5g/min) molar ratio, the requirement of residence time 0.5s, under normal pressure, while by chlorine
Gas and pyrolysis product are delivered in shell and tube reactor 2.Reaction product is collected through condensation, obtains chlorizate.Sampled analysis,
98.8%, 1,1,1,2,3- pentachloro- third of tri chloropropene (1,1,3- tri chloropropene/3,3,3- tri chloropropene) conversion ratio can be observed
Alkane (HCC-240db) selectivity 99.3%.
(8) shell and tube reactor 3 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 5mm, long 45cm, single tube totally 30.Temperature rise in shell and tube reactor is then passed through into metering to 450 DEG C in advance
Chlorizate normal pressure is passed through by pump with the flow velocity of 1.5g/min, and residence time 8s, mixture is condensed, and HCl tail gas is removed, through removing
Moisture content is controlled after water, and 1,1,2,3- tetrachloropropylene (TCP) is then obtained by rectifying column rectifying, passes through sampling analysis, observable
It is 69% to conversion ratio, 98.4% (being calculated on the basis of HCC-240db) of selectivity.
Embodiment 5
(1) synergist containing neodymium is prepared
By weight, it with the ZSM-5 molecular sieve that 100 parts are added in stirred reactor, adds water and stirs to obtain slurries, dropwise
300 parts of methanol that mass concentration is 40%, filtering are added, washing filter cake to neutrality is dried, and 400 DEG C of roasting 6h are put into flask
In, it adds 0.6 part of hexafluorophosphoric acid iron of three (1,10- phenanthroline), 400 parts of acetone, hexafluoro -2,4- acetylacetone,2,4-pentanedione neodymium (III) two
0.3 part of hydrate, 5 parts of amine zinc of bis- (double trimethyl silicon substrates) 5 parts of alkyl imidazoline phosphate, are stirred to react 2h, are filtered, and dry
It is dry, synergist containing neodymium is made, it is spare.
(2) carbon tetrachloride mixed liquor is prepared
Carbon tetrachloride is added in synergist containing neodymium, auxiliary agent tributyl phosphate, the 200 mesh iron powder of catalyst that step (1) is obtained
In, it is uniformly mixing to obtain carbon tetrachloride mixed liquor, the content of the synergist containing neodymium is 0.5wt%, phosphoric acid in carbon tetrachloride mixed liquor
The content of tributyl is 1.0wt%, and the content of iron powder is 1.0wt%, spare.
(3) kettle nitrogen replacement will be reacted twice, and will then raise temperature to 110 DEG C, and be 2 according to carbon tetrachloride and ethylene molar ratio,
Carbon tetrachloride mixed liquor and ethylene two streams are passed through in reaction kettle simultaneously respectively, and pass through by the requirement of residence time 90min
Constant flow pump and mass flowmenter control respective flow.At the same time, the continuous constant speed drainage of discharging mouth containing HCC-250fb reaction solution,
Maintenance system pressure 1.0Mpa, continuous sampling analysis.It can be observed to calculate on the basis of ethylene, conversion ratio 99.6%, HCC-
250fb selectivity 99.0%.
(4) reaction solution containing HCC-250fb is continuously conveyed with the flow of 40ml/min to the first UF membrane by constant flow pump
In device, the first membrane separator membrane area 0.4m2, operating pressure 0.8Mpa, 30 DEG C of operation temperature.After separation, HCC-250fb is anti-
Liquid is answered to be divided into the non-polar materials such as carbon tetrachloride (logistics 1) and HCC-250fb/ auxiliary agent/two strands of objects of catalyst mixture (logistics 2)
Stream.By sampling analysis, logistics 1 can be observed and form (mass percentage) are as follows: 90% carbon tetrachloride, 8%HCC-250fb,
1.5% tetrachloro-ethylene, 0.5% carbon trichloride.Logistics 2 forms (mass percentage) are as follows: 92%HCC-250fb, catalyst
2%, synergist containing neodymium 2.5%, 1.5% carbon tetrachloride, 1.0% carbon trichloride, 1,1,1,5- tetra- chloropentane 1.0%.Logistics 2 is logical
It crosses pump to be continuously conveyed with 20ml/min flow velocity into the second membrane separator, membrane area 0.2m2, operating pressure 1.2Mpa, operation temperature
30 DEG C of degree, logistics 2 is divided into the mixtures such as the mixtures such as HCC-250fb (logistics 3) and catalyst/synergist containing neodymium (logistics 4)
Two streams.By sampling analysis, logistics 3 can be observed and form (mass percentage) are as follows: 92%HCC-250fb, 7% tetrachloro
Change carbon, 0.5% carbon trichloride, other 0.5%.Logistics 4 forms (mass percentage) are as follows: 5%HCC-250fb, 4% 4 chlorination
Carbon, 2% carbon trichloride, 1,1,1,5- tetra- chloropentane 3%, catalyst quality 11%, the quality of synergist containing neodymium 75%.Logistics 4 can
It continues cycling through and applies, to avoid some such as 1,1,1,5- tetra- chloropentanes of heavy by-product etc. from accumulating, logistics 4 is carried out continuously or periodically
Part remove.The material cleared out of can carry out batch fractionating, further to recycle useful object therein.
(5) logistics 1 and 3 mixed liquor of logistics are delivered in rectifying knockout tower, which is provided with the condenser of cooling water,
3L round-bottomed flask reboiler, packed height 1.5m, using oil bath heating, reflux ratio uses 4, and reboiler temperature is risen to by 124 DEG C
158 DEG C of end.Overhead light (predominantly carbon tetrachloride) is recycled to step (2) reuse, and tower bottom is the centre containing HCC-250fb
1,1,1,3- tetrachloro propane content (HCC-250fb) 99.6wt% can be observed by sampling analysis intermediate in body.
(6) shell and tube reactor 1 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 8mm, long 35cm, single tube totally 20.Temperature rise in shell and tube reactor is then passed through into metering to 450 DEG C in advance
Intermediate containing HCC-250fb is passed through shell and tube reactor 1 with the flow velocity of 1g/min by pump, residence time 3s, and mixture is cold through 1
It is solidifying, HCl tail gas is removed, pyrolysis product is obtained.By sampling analysis, HCC-250fb conversion ratio 97%, tri chloropropene can be observed
(1,1,3- tri chloropropene/3,3,3- tri chloropropene) selectivity 99%.
(7) shell and tube reactor 2 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 6mm, long 50cm, single tube totally 40.Temperature rise in shell and tube reactor is then passed through into metering to 140 DEG C in advance
Pump is 1.2 according to chlorine and pyrolysis product (1.5g/min) molar ratio, the requirement of residence time 0.8s, under normal pressure, while by chlorine
Gas and pyrolysis product are delivered in shell and tube reactor 2.Reaction product is collected through condensation, obtains chlorizate.Sampled analysis,
99.4%, 1,1,1,2,3- pentachloro- third of tri chloropropene (1,1,3- tri chloropropene/3,3,3- tri chloropropene) conversion ratio can be observed
Alkane (HCC-240db) selectivity 99.6%.
(8) shell and tube reactor 3 (including preheating zone 1/5, reaction zone 3/5, cool down outlet area 1/5) is added using molten salt bath
Heat, single tube internal diameter 5mm, long 45cm, single tube totally 30.Temperature rise in shell and tube reactor is then passed through into metering to 430 DEG C in advance
Chlorizate normal pressure is passed through by pump with the flow velocity of 1.5g/min, and residence time 5s, mixture is condensed, and HCl tail gas is removed, through removing
1,1,2,3- tetrachloropropylene (TCP) is obtained by rectifying column rectifying after water, by sampling analysis, conversion ratio, which can be observed, is
66%, 98.8% (being calculated on the basis of HCC-240db) of selectivity.
Claims (10)
1. the preparation method of 1,1,2,3- tetrachloropropylene of one kind, which comprises the following steps:
(1) by weight, 100 parts of molecular sieve is added in the first reactor, adds water and stirs to obtain slurries, adds methanol-water
150-300 parts of solution, filtering, washing filter cake to neutrality is dried, then three (1,10- phenanthroline) hexafluorophosphoric acid iron are added in roasting
0.05-0.7 parts, 200-500 parts of acetone, 0.02-0.5 parts of (III) dihydrate of hexafluoro -2,4- acetylacetone,2,4-pentanedione neodymium, bis- (double front threes
Base silicon substrate) 1-8 parts of amine zinc, 5-20 parts of alkyl imidazoline phosphate, 2-6h is reacted, is filtered, drying obtains synergist containing neodymium, standby
With；
(2) synergist containing neodymium, tributyl phosphate, the iron powder obtained step (1) is added in carbon tetrachloride, is uniformly mixing to obtain four
Chlorination carbon mixed liquor, the content of the synergist containing neodymium is 0.5-2.5wt% in the carbon tetrachloride mixed liquor, and tributyl phosphate contains
Amount is 0.5-1.0wt%, and the content of iron powder is 0.5-1.0wt%, spare；
(3) the carbon tetrachloride mixed liquor that step (2) obtains continuously is passed through in second reactor with ethylene and is reacted, it is described anti-
The temperature answered is 90-120 DEG C, residence time 1-2h, system pressure 0.5-1.0Mpa, and carbon tetrachloride is with ethylene molar ratio
1-4:1 obtains the first reaction product；
(4) the first reaction product that step (3) obtains is passed through in the first membrane separator, the first logistics and second is obtained after separation
Logistics, the second logistics is passed through in the second membrane separator, and third―party logistics and the 4th logistics are obtained after separation；
(5) the first logistics and third―party logistics obtained step (4) carries out rectifying, obtains 1,1,1,3- tetra- chloropropane and recycling
Carbon tetrachloride；
(6) 1,1,1,3- tetra- chloropropane for obtaining step (5) carries out cracking reaction, and the temperature of the cracking reaction is 350-
500 DEG C, residence time 1-8s, pyrolysis product is obtained after condensing and separating tail gas；
(7) pyrolysis product for obtaining step (6) carries out gas phase chlorination, and the temperature of the gas phase chlorination is 140-170 DEG C, stops
Time is 0.5-5.5s, and the molar ratio of chlorine and pyrolysis product is 1-4:1, and gas phase chlorination is obtained after condensing and separating tail gas and is produced
Object；
(8) the gas phase chlorination product that step (7) obtains is cracked, the temperature of the cracking is 350-500 DEG C, the residence time
For 2-15s, collecting reaction product condensation, rectifying obtain 1,1,2,3- tetrachloropropylene products.
2. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (1)
Methanol aqueous solution mass concentration be 20-40%.
3. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (1)
Roasting temperature be 400-600 DEG C, time 2-6h.
4. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (1)
Molecular sieve be ZSM-5 molecular sieve.
5. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (2)
Iron powder be 80-200 mesh.
6. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (4)
First membrane separator operating pressure is 0.5-1.0Mpa, and operation temperature is 15-40 DEG C, and the second membrane separator operating pressure is 1.0-
1.5Mpa, operation temperature are 25-60 DEG C.
7. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that obtain step (4)
The 4th logistics carry out rectifying, to recycle synergist containing neodymium therein.
8. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (5)
Rectifying temperature be 120-160 DEG C, reflux ratio 2-6.
9. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that by institute in step (5)
The carbon tetrachloride for the recycling stated is returned in step (2) and is recycled.
10. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (7)
Residence time be 0.5-1s.
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|---|---|---|---|---|
| CN116003256A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | System for purifying and preparing methyl methacrylate and method for purifying methyl methacrylate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725487A (en) * | 1970-04-13 | 1973-04-03 | Celanese Corp | Preparation of dihaloalkanes and related products |
| CN104130100A (en) * | 2007-12-19 | 2014-11-05 | 西方化学股份有限公司 | Methods of making chlorinated hydrocarbons |
| CN105026346A (en) * | 2013-02-04 | 2015-11-04 | 霍尼韦尔国际公司 | Synthesis of 1,1,2,3-tetrachloropropene |
| CN107001190A (en) * | 2014-10-16 | 2017-08-01 | 化学和冶金生产联合体股份公司 | Method |
| CN109796300A (en) * | 2018-12-29 | 2019-05-24 | 浙江巨化技术中心有限公司 | A kind of continuous preparation method of 2,3,3,3- tetrafluoropropene |
-
2019
- 2019-08-16 CN CN201910758215.2A patent/CN110511112A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725487A (en) * | 1970-04-13 | 1973-04-03 | Celanese Corp | Preparation of dihaloalkanes and related products |
| CN104130100A (en) * | 2007-12-19 | 2014-11-05 | 西方化学股份有限公司 | Methods of making chlorinated hydrocarbons |
| CN105026346A (en) * | 2013-02-04 | 2015-11-04 | 霍尼韦尔国际公司 | Synthesis of 1,1,2,3-tetrachloropropene |
| CN107001190A (en) * | 2014-10-16 | 2017-08-01 | 化学和冶金生产联合体股份公司 | Method |
| CN109796300A (en) * | 2018-12-29 | 2019-05-24 | 浙江巨化技术中心有限公司 | A kind of continuous preparation method of 2,3,3,3- tetrafluoropropene |
Non-Patent Citations (2)
| Title |
|---|
| 曾纪珺等: "FeCl3/磷酸三丁酯催化四氯化碳与氯乙烯的调聚反应:结构与活性", 《分子催化》 * |
| 许晓涛等: "铁粉催化合成1,1,1,3,3-五氯丙烷", 《化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003256A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | System for purifying and preparing methyl methacrylate and method for purifying methyl methacrylate |
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