CN105859512A - Preparation method of 1,1,1,3, 3-pentachloropropane - Google Patents
Preparation method of 1,1,1,3, 3-pentachloropropane Download PDFInfo
- Publication number
- CN105859512A CN105859512A CN201610247011.9A CN201610247011A CN105859512A CN 105859512 A CN105859512 A CN 105859512A CN 201610247011 A CN201610247011 A CN 201610247011A CN 105859512 A CN105859512 A CN 105859512A
- Authority
- CN
- China
- Prior art keywords
- pentachloropropane
- carbon tetrachloride
- vinyl chloride
- tower
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 80
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000199 molecular distillation Methods 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 claims description 5
- WZPMZMCZAGFKOC-UHFFFAOYSA-N diisopropyl hydrogen phosphate Chemical compound CC(C)OP(O)(=O)OC(C)C WZPMZMCZAGFKOC-UHFFFAOYSA-N 0.000 claims description 5
- -1 1,1,1,3,3-pentachloro- Bromopropane Chemical compound 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical group CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 24
- 238000002156 mixing Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 26
- 239000002994 raw material Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 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 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
- FHDBYEQPLDIGTD-UHFFFAOYSA-N CCCC.[Cl] Chemical compound CCCC.[Cl] FHDBYEQPLDIGTD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005796 dehydrofluorination reaction 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
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 235000015114 espresso Nutrition 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 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
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- 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
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/42—Tin
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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 preparation method of 1,1,1,3, 3-pentachloropropane, which comprises the following steps: (1) mixing carbon tetrachloride, chloroethylene and a catalyst, and then continuously introducing the mixture into a reactor for reaction to obtain a mixture containing 1,1,1,3, 3-pentachloropropane and unreacted carbon tetrachloride; (2) continuously introducing a mixture containing 1,1,1,3, 3-pentachloropropane and unreacted carbon tetrachloride into a first rectifying tower for rectification, obtaining the unreacted carbon tetrachloride at the tower top, circulating the unreacted carbon tetrachloride back to a reactor, and obtaining a mixture containing 1,1,1,3, 3-pentachloropropane at the tower bottom; (3) separating the mixture obtained in the step (2) to obtain inorganic salt and a product containing 1,1,1,3, 3-pentachloropropane; (4) and (4) continuously introducing the product containing the 1,1,1,3, 3-pentachloropropane obtained in the step (3) into a second rectifying tower for rectification to obtain a 1,1,1,3, 3-pentachloropropane product. The method has the advantages of simple process, low energy consumption, high reaction efficiency, safety, environmental protection and continuous operation.
Description
Technical field
The present invention relates to the preparation method of halogenated hydrocarbons, relate more specifically to the preparation method of a kind of 1,1,1,3,3-pentachloropropane.
Background technology
1,1,1,3,3-pentachloropropane (HCC-240fa) is the important intermediate preparing 1,1,1,3,3-pentafluoropropane.1,1,1,3,3-
Pentafluoropropane (HFC-245fa) has the most excellent physical property, has and is quite widely applied, can be used for hard
Polyurethane and the foaming of polyisocyanurate foam ambroin, it is possible to replace CFC-11, CFC-12, HCFC-141b to use
Make foaming agent and cold-producing medium, abluent, heat-conduction medium, the aerosol propellants etc. not damaged the ozone layer.Pass through
The HFC-245fa that HCC-240fa prepares, then carry out dehydrofluorination, low global warming potential can be prepared
The 1 of (GWP value), 3,3,3-tetrafluoropropenes (HFO-1234ze), HFO-1234ze is considered as to substitute HFC-134a etc.
Good succedaneum for foaming agent, cold-producing medium and aerosol propellants.Also may be used with HCC-240fa and HF for raw material
Prepared the 1-chloro-3,3,3 ,-trifluoropropene (HFO-1233zd) of lower GWP value by fluorination reaction, HFO-1233zd can answer
For foaming, freezing, the field such as cleaning.Further, HFO-1234ze and HFO-1233zd also acts as fluorine-containing poly-
Monomer adduct.
Preparation 1,1,1,3,3-pentachloropropane method have a lot, mainly the change of the change on process route and catalyst with
And structure of reactor form is different.According to the difference of raw material, the route of preparation 1,1,1,3,3-pentachloropropane mainly has following three
Bar:
(1) with l, 1-dichloroethylene and carbon tetrachloride are raw material, by addition, elimination, hydrogenating reduction counter become generation 1,1,1,3,3-
Pentachloropropane.
(2) with ethylene and carbon tetrachloride as raw material, 1 is prepared through addition, light chlorination, 1,1,3,3-pentachloropropane.
(3) with vinyl chloride and carbon tetrachloride as raw material, 1,1,1,3,3-pentachloropropane is generated through additive reaction.
In above-mentioned three synthetic routes, l, the 2nd article of synthetic route are all multi-step synthetic method.Step due to reaction
Many, the raw-material input of production process can be increased, produce the input of equipment, the input of personnel and the input of environmental protection treatment,
So that production and operation cost increases.
Article 3, synthetic route is the reaction scheme that current employing is most, and raw material is easier to obtain, and synthesis technique is simple.
With vinyl chloride and carbon tetrachloride as raw material, according to the difference of catalyst, mainly have copper-amine catalyst telomerization synthesis technique and
Ferrum-phosphide catalyst telomerization synthesis technique.Copper-amine catalyst corrosivity is relatively strong, and product viscosity is relatively big, is unfavorable for that serialization is grasped
Make.
With vinyl chloride and carbon tetrachloride as raw material, the telomerisation mechanism related to is as follows:
Main by-product reaction equation:
CCl3CH2CHCl2+CH2=CHCl → CCl3CH2CHCICH2CHCl2(HCC-470jfdf)
CCl3CH2CHCl2+CH2=CHCl → CHCl2CH2CCl2CH2CHCl2(HCC-470nfaf)
The very small amount high-boiling components that reaction produces is mainly HCC-470 (1,1,1,3,5,5-chlordene pentane and 1,1,3,3,5,5-chlordene
Pentane) and very small amount vinyl chloride autohemagglutination matter PVC.
Chinese patent CN103608319A discloses and avoids by-product to generate in compound halo alkane production process
Method, in the method, vinyl chloride is fed into is preinstalled with material by immersion pipe or sponge type gaseous diffuser in vapour form
In reactor, it is to avoid the generation of polrvinyl chloride.The method immersion pipe or sponge type gaseous diffuser are placed in reactor, temperature
Spending more than 80 DEG C, vinyl chloride is easy to autohemagglutination at such a temperature, is actually difficult to play anti-autohemagglutination effect.
Patent CN103274893A discloses 1, the preparation method of 1,1,3,3-pentachloropropane, the method use ferrum, iron chloride,
Triethyl phosphate is passed through in reactor after adding carbon tetrachloride tank preparation catalyst mixture.Triethyl phosphate, tricresyl phosphate fourth
Ester easily resolves into the most stable diethyl phosphate, dibutylphosphoric acid ester more than 100 DEG C, and discharges ethyl chloride, chlorine
Butane.Additionally, iron chloride is a kind of lewis acid, system corrosivity can be strengthened, be unfavorable for serialization stable operation.
Patent CN104230648A discloses 1, the preparation technology of 1,1,3,3-pentachloropropane, and before reaction, reactor heats up, instead
Should lower the temperature by reactor afterwards, for andnon-continuous operation manner, waste energy consumption and reaction efficiency are low.
Patent CN104230649A discloses pentachloropropane preparation method, washes and dry back after the method catalyst filtration
Receiving, actually add water and catalyst can be caused to be destroyed, reclaimer operation is complicated.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that it is a kind of that technique is simple, energy consumption is low, reaction efficiency is high, safety and environmental protection,
Can the preparation method of 1,1,1,3,3-pentachloropropane of continuous operation.
To achieve these goals, the technical solution used in the present invention is: the preparation method of a kind of 1,1,1,3,3-pentachloropropane,
Comprise the following steps:
(1) it is passed through reactor after carbon tetrachloride, vinyl chloride being mixed with catalyst continuously to react, is contained
The mixture of 1,1,1,3,3-pentachloropropane, unreacted carbon tetrachloride completely, described vinyl chloride with carbon tetrachloride mol ratio is
1:3～6, described catalyst amount is the 0.01～7% of vinyl chloride weight, and reaction temperature is 70～180 DEG C, when reaction stops
Between be 0.1～4.0h；
(2) mixture containing 1,1,1,3,3-pentachloropropane, unreacted carbon tetrachloride completely step (1) obtained is even
Continuous being passed through the first rectifying column and carry out rectification, tower top obtains unreacted carbon tetrachloride completely, is recycled back in reactor,
Tower reactor obtains containing 1, the mixture of 1,1,3,3-pentachloropropane, and described first tower bottom of rectifying tower temperature is 60～170 DEG C, pressure
For-0.085～-0.095MPa；
(3) tower reactor mixture isolated inorganic salt step (2) obtained and the product containing 1,1,1,3,3-pentachloropropane；
(4) step (3) is obtained containing 1, the product of 1,1,3,3-pentachloropropane is passed through Second distillation column continuously and carries out rectification,
Described Second distillation column bottom temperature is 40～150 DEG C, and pressure is-0.050～-0.099MPa, obtains 1,1,1,3,3-pentachloro-
Bromopropane product.
For improving selectivity and the conversion rate of vinyl chloride of target product, it is to avoid high-boiling components is formed, as the preferred reality of the present invention
Execute mode, described carbon tetrachloride can be led to as one logistics after catalyst, vinyl chloride premixing by step (1)
Enter and reactor carries out successive reaction.Compare carbon tetrachloride and vinyl chloride separately charging, use this kind of feeding mode to avoid
The highest heat of vinyl chloride makes vinyl chloride autohemagglutination block pipeline, improves vinyl chloride dispersion in the reactor simultaneously,
Further increase target product yield, decrease many carbon halogenated hydrocarbons HCC-470 and vinyl chloride autohemagglutination matter PVC from source
Generate.
Described catalyst is preferably made up of major catalyst and auxiliary agent, and described major catalyst and auxiliary agent mol ratio are 1:0.5～3.
Described major catalyst is preferably two kinds in ferrum, stannum, nickel, zinc, magnesium, can more effectively improve mesh than single catalyst
Mark selectivity of product；The preferred NSC 5284 of auxiliary agent, diisopropyl phosphate, tributyl phosphite, dibutyl phosphite,
The mixture of one or more in dibutylphosphoric acid ester, dimethylformamide, the mixture of multiple auxiliary agent is than single auxiliary agent energy
It is greatly promoted major catalyst to dissolve, improves the catalyst dissolubility in this system, therefore auxiliary agent more preferably tricresyl phosphite second
In ester, diisopropyl phosphate, tributyl phosphite, dibutyl phosphite, dibutylphosphoric acid ester, dimethylformamide many
The mixture planted.
Vinyl chloride described in step (1) and carbon tetrachloride mol ratio are preferably 1:3～5, and described catalyst amount is preferably chlorine
The 1～5% of weight ethylene, reaction temperature is preferably 80～120 DEG C, and reaction time is preferably 0.5～2.0h.
The first tower bottom of rectifying tower temperature described in step (2) is preferably 90～115 DEG C, pressure be preferably-0.088～
-0.095MPa。
Second distillation column bottom temperature described in step (4) is preferably 45～70 DEG C, pressure be preferably-0.085～
-0.099MPa。
Described Second distillation column is preferably molecular distillation tower.
The present invention uses carbon tetrachloride and vinyl chloride to be raw material, prepares 1 by Radical Addition, 1,1,3,3-pentachloro-third
Alkane.The present invention uses continuous operation, it is to avoid heating and cooling waste energy consumption, realizes efficiently producing simultaneously.
The present invention forms complex for making major catalyst and auxiliary agent fully react dissolving, use promoter little over metering method,
Preferably major catalyst and auxiliary agent mol ratio are 1:0.5～3；Preferred catalyst consumption is the 0.01～7% of vinyl chloride weight, enters
One step preferred catalyst consumption is the 1～5% of vinyl chloride weight.
The present invention uses the method for carbon tetrachloride excess, makes vinyl chloride reach to compare uniform state, advantageously reduces by-product
Being formed, therefore, in the present invention, vinyl chloride and carbon tetrachloride mol ratio are that 1:3～6, preferably vinyl chloride rub with carbon tetrachloride
That ratio is 1:3～5.In the present invention, reactor reaction temperature is 70～180 DEG C, preferably 80～120 DEG C.
In the present invention, not limiting reaction pressure, as long as vinyl chloride mixing is preferably, reaction pressure may remain in more steady
In the range of Ding, and pressure height is to target product 1, and 1,1,3,3-pentachloropropane yield the most significantly affects.This telomerisation
For radical reaction, response speed is very fast, for be prevented effectively from 1,1,1,3,3-pentachloropropane of generation further with vinyl chloride
Reaction generates HCC-470 high-boiling components, and in the present invention, material time of staying in reactor is 0.1～4.0h, is preferably
0.5～2.0h.
What telomerisation obtained reclaims the carbon tetrachloride of excess to instead by the first rectifying tower top again containing HCC-240fa logistics
Device, tower reactor is answered to obtain rich 1,1,1,3,3-pentachloropropane stream stock.First rectification tower reactor temperature control is 60～170 DEG C, and pressure is
-0.085～-0.095MPa, preferably still temperature is 90～115 DEG C, and pressure is-0.088～-0.095MPa.
For reducing for 1,1,1,3,3-pentachloropropane time of staying in Second distillation column, it is to avoid dehydrochlorination decomposition reaction occurs,
And avoid still-process generation bubbling and mass transport process reversible etc., improve product yield in separation process, reduce energy consumption, this
Second distillation column in invention preferably employs molecular distillation tower.Molecular distillation is a kind of special liquid--liquid isolation technics, it
It is different from Conventional espresso and relies on boiling-point difference separation principle, but the difference by different material molecular tools realizes
Separate.At a certain temperature, pressure is the lowest, and the mean free path of gas molecule is the biggest.When the pressure of evaporating space is the lowest
(10-2～10-4MmHg), and making condensing surface near evaporating surface, vertical dimension therebetween is less than the flat of gas molecule
All during free path, from the vapour molecule of evaporating surface vaporization, can not directly arrive condensing surface with other molecular collisions
And condense.Molecular distillation process is: material adds from the top of vaporizer, and the liquid distributor on rotor is continuous by it
Being evenly distributed on heating surface, feed liquid is spread to one layer of very thin, liquid film in turbulence-like by blade applicator immediately, and with spiral
Shape advances downwardly.In the process, light molecule 1,1,1,3, the 3-pentachloropropane of effusion from heating surface, through too short route
Almost arrive without collision and be condensed into liquid on built-in condenser, and flow down along condenser tube, by being positioned at base of evaporator
Discharge nozzle discharge i.e. can get target product 1,1,1,3,3-pentachloropropane；The i.e. weight molecule HCC-470 of residual liquid is in the thermal treatment zone
Under circular channel in collect, then by the discharge nozzle of side flows out.Middle molecule distillation column bottom temperature of the present invention is
40～150 DEG C, pressure is-0.050～-0.099MPa, preferably controls temperature 45 C～70 DEG C, pressure be-0.085～
-0.099MPa.Molecular distillation tower advantage is that control temperature is low, and 1,1,1,3,3-pentachloropropane is short at dwell time in the tower, keeps away
Exempt from dehydrochlorination decomposition reaction, improve product yield in separation process, and have that energy consumption is low, still-process is not sent out
The advantages such as raw bubbling, mass transport process are irreversible, are suitable for similar temperature higher than 120 DEG C of 1 decomposed, 1,1,3,3-pentachloro-third
Alkane heat-sensitive substance separates.
Compared with prior art, the invention have the advantages that
1, technique is simple, and energy consumption is low, it is achieved that the continuous production of 1,1,1,3,3-pentachloropropane；
2, reaction efficiency is high, and VCM conversion ratio is 100%, and HCC-240fa selectivity is more than 99.5%.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
As shown in the figure: 1 is mixing channel, 2 is reactor, and 3 is the first rectifying column, and 4 is separator, and 5 is the second rectification
Tower, 6,7,8,9,10,11,12,13 is pipeline.
Detailed description of the invention
Flow process of the present invention is as it is shown in figure 1, major catalyst, auxiliary agent, fresh carbon tetrachloride and vinyl chloride (VCM) are passed through
After mixing channel 1 mix homogeneously, enter reactor 2 by pipeline 6 and react, containing 1,1,1,3,3-pentachloropropane, catalyst,
The product of the carbon tetrachloride of very small amount high-boiling components HCC-470 and excess is directly entered the first rectifying column 3 through pipeline 7.
The material of the first rectifying column 3 top exit is unreacted carbon tetrachloride completely, and through pipeline 8, it is recycled to reactor 2
Continuing reaction, the first rectifying column 3 bottom obtains containing 1,1,1,3,3-pentachloropropane, catalyst, very small amount high-boiling components HCC-470
Deng mixture, it is entered separator 4 through pipeline 9 and obtains inorganic salt and rich 1,1,1,3,3-pentachloropropane logistics.Inorganic
Salt is otherwise processed after pipeline 10 is collected, and rich 1,1,1,3,3-pentachloropropane logistics enters Second distillation column 5 through pipeline 11.
Obtaining target product 1,1,1,3,3-pentachloropropane from Second distillation column 5 bottom line 13, diapire pipeline 12 discharging obtains seldom
Amount high-boiling components HCC-470.
Below by embodiment, the present invention is described in further detail, but the present invention is not limited to described embodiment.
Embodiment 1
Add mixing channel 1 (material 304,2m3) vinyl chloride and carbon tetrachloride mol ratio be 1:3, catalyst amount is
The 0.3% of vinyl chloride weight, catalyst composition and mol ratio (mol/mol) are ferrum: stannum: diisopropyl phosphate=1:0.25:1；Instead
The reaction temperature answering device 2 (material enamel, 400L) is 90 DEG C, and the material time of staying in reactor 2 is 2.0h；
First rectifying column 3 bottom temperature is 80 DEG C, and pressure is-0.095MPa；(molecular distillation tower, is purchased from Second distillation column 5
Jiangsu Maike Chemical Machinery Co., Ltd.) bottom temperature is 40 DEG C, pressure is-0.099MPa.Take in reactor 2 outlet
The sample composition of chromatographic organic product, calculates conversion rate of vinyl chloride and target product HCC-240fa selects
Property, the results are shown in Table 1.Export sample analysis at Second distillation column 5 bottom discharge pipe, the results are shown in Table 1.
Embodiment 2
Add mixing channel 1 (material 304L, 2m3) vinyl chloride and carbon tetrachloride mol ratio be 1:4, catalyst amount is
The 0.6% of vinyl chloride weight, catalyst composition and mol ratio (mol/mol) are magnesium: stannum: NSC 5284=1:0.25:3.75；
The reaction temperature of reactor 2 (material 316L, 400L) is 110 DEG C, and the material time of staying in reactor 2 is 1.6
h；First rectifying column 3 bottom temperature is 90 DEG C, and pressure is-0.094MPa；(molecular distillation tower, purchases Second distillation column 5
From Jiangsu Maike Chemical Machinery Co., Ltd.) bottom temperature is 50 DEG C, pressure is-0.97MPa.Take in reactor 2 outlet
The sample composition of chromatographic organic product, calculates conversion rate of vinyl chloride and target product HCC-240fa selects
Property, the results are shown in Table 1.Export sample analysis at Second distillation column 5 bottom discharge pipe, the results are shown in Table 1.
Embodiment 3
Add mixing channel 1 (material 304,2m3) vinyl chloride and carbon tetrachloride mol ratio be 1:4, catalyst amount is
The 1.5% of vinyl chloride weight, catalyst composition and mol ratio (mol/mol) are ferrum: nickel: tributyl phosphite=1:0.25:2；Instead
The reaction temperature answering device 2 (material 304L, 400L) is 115 DEG C, and the material time of staying in reactor 2 is 1.4h；
First rectifying column 3 bottom temperature is 100 DEG C, and pressure is-0.093MPa；(molecular distillation tower, is purchased from Second distillation column 5
Jiangsu Maike Chemical Machinery Co., Ltd.) bottom temperature is 55 DEG C, pressure is-0.096MPa.Take in reactor 2 outlet
The sample composition of chromatographic organic product, calculates conversion rate of vinyl chloride and target product HCC-240fa selects
Property, the results are shown in Table 1.Export sample analysis at Second distillation column 5 bottom discharge pipe, the results are shown in Table 1.
Embodiment 4
Add mixing channel 1 (material 316L, 2m3) vinyl chloride and carbon tetrachloride mol ratio be 1:5, catalyst amount is
The 2.0% of vinyl chloride weight, catalyst composition and mol ratio (mol/mol) are zinc: nickel: dibutyl phosphite=1:0.25:3；Instead
The reaction temperature answering device 2 (material enamel, 400L) is 120 DEG C, and the material time of staying in reactor 2 is 1.0h；
First rectifying column 3 bottom temperature is 110 DEG C, and pressure is-0.090MPa；(molecular distillation tower, is purchased from Second distillation column 5
Jiangsu Maike Chemical Machinery Co., Ltd.) bottom temperature is 55 DEG C, pressure is-0.093MPa.Take in reactor 2 outlet
The sample composition of chromatographic organic product, calculates conversion rate of vinyl chloride and target product HCC-240fa selects
Property, the results are shown in Table 1.Export sample analysis at Second distillation column 5 bottom discharge pipe, the results are shown in Table 1.
Embodiment 5
Add mixing channel 1 (material 304,2m3) vinyl chloride and carbon tetrachloride mol ratio be 1:6, catalyst amount is
The 3.5% of vinyl chloride weight, catalyst composition and mol ratio (mol/mol) are ferrum: stannum: diisopropyl phosphate: dimethylformamide
=1:0.25:0.75:0.75；The reaction temperature of reactor 2 (material 304L, 400L) is 120 DEG C, and material is at reactor 2
In the time of staying be 0.8h；First rectifying column 3 bottom temperature is 120 DEG C, and pressure is-0.088MPa；Second rectification
Tower 5 (molecular distillation tower, purchased from Jiangsu Maike Chemical Machinery Co., Ltd.) bottom temperature is 60 DEG C, and pressure is-0.093MPa.
Export the composition of sampling chromatographic organic product at reactor 2, calculate conversion rate of vinyl chloride and target product
HCC-240fa selectivity, the results are shown in Table 1.Export sample analysis at Second distillation column 5 bottom discharge pipe, the results are shown in Table
1。
Embodiment 6
Add mixing channel 1 (material 304,2m3) vinyl chloride and carbon tetrachloride mol ratio be 1:4, catalyst amount is
The 5.0% of vinyl chloride weight, catalyst composition and mol ratio (mol/mol) are ferrum: stannum: dibutylphosphoric acid ester: dimethylformamide
=1:0.25:0.75:0.75；The reaction temperature of reactor 2 (material 316,400L) is 125 DEG C, and material is at reactor 2
In the time of staying be 0.4h；First rectifying column 3 bottom temperature is 125 DEG C, and pressure is-0.87MPa；Second distillation column
5 (molecular distillation tower, purchased from Jiangsu Maike Chemical Machinery Co., Ltd.) bottom temperature is 65 DEG C, and pressure is-0.092MPa.
Export the composition of sampling chromatographic organic product at reactor 2, calculate conversion rate of vinyl chloride and target product
HCC-240fa selectivity, the results are shown in Table 1.Export sample analysis at Second distillation column 5 bottom discharge pipe, the results are shown in Table
1。
Embodiment 7
Add mixing channel 1 (material 304,2m3) vinyl chloride and carbon tetrachloride mol ratio be 1:4, catalyst amount is
The 7.0% of vinyl chloride weight, catalyst composition and mol ratio (mol/mol) they are ferrum: stannum: dibutylphosphoric acid ester: dimethylformamide:
Dibutyl phosphite=1:0.25:0.75:0.75:0.75；The reaction temperature of reactor 2 (material 304L, 400L) is 130
DEG C, the material time of staying in reactor 2 is 0.1h；First rectifying column 3 bottom temperature is 130 DEG C, and pressure is
-0.085MPa；Second distillation column 5 (molecular distillation tower, purchased from Jiangsu Maike Chemical Machinery Co., Ltd.) bottom temperature is
70 DEG C, pressure is-0.090MPa.The composition of sampling chromatographic organic product is exported, meter at reactor 2
Calculate conversion rate of vinyl chloride and target product HCC-240fa selectivity, the results are shown in Table 1.At Second distillation column 5 bottom discharge
Pipe outlet sample analysis, the results are shown in Table 1.
Table 1 embodiment 1～7 implementation result and product analysis result
Claims (7)
1. one kind 1, the preparation method of 1,1,3,3-pentachloropropane, it is characterised in that comprise the following steps:
(1) it is passed through reactor after carbon tetrachloride, vinyl chloride being mixed with catalyst continuously to react, is contained
The mixture of 1,1,1,3,3-pentachloropropane, unreacted carbon tetrachloride completely, described vinyl chloride with carbon tetrachloride mol ratio is
1:3～6, described catalyst amount is the 0.01～7% of vinyl chloride weight, and reaction temperature is 70～180 DEG C, when reaction stops
Between be 0.1～4.0h；
(2) mixture containing 1,1,1,3,3-pentachloropropane, unreacted carbon tetrachloride completely step (1) obtained is even
Continuous being passed through the first rectifying column and carry out rectification, tower top obtains unreacted carbon tetrachloride completely, is recycled back in reactor,
Tower reactor obtains containing 1, the mixture of 1,1,3,3-pentachloropropane, and described first tower bottom of rectifying tower temperature is 60～170 DEG C, pressure
For-0.085～-0.095MPa；
(3) tower reactor mixture isolated inorganic salt step (2) obtained and the product containing 1,1,1,3,3-pentachloropropane；
(4) step (3) is obtained containing 1, the product of 1,1,3,3-pentachloropropane is passed through Second distillation column continuously and carries out rectification,
Described Second distillation column bottom temperature is 40～150 DEG C, and pressure is-0.050～-0.099MPa, obtains 1,1,1,3,3-pentachloro-
Bromopropane product.
The preparation method of 1,1,1,3,3-pentachloropropane the most according to claim 1, it is characterised in that described catalysis
Agent is made up of major catalyst and auxiliary agent, and described major catalyst and auxiliary agent mol ratio are 1:0.5～3.
The preparation method of 1,1,1,3,3-pentachloropropane the most according to claim 1, it is characterised in that described sponsors
In agent chosen from Fe, stannum, nickel, zinc, magnesium two kinds, auxiliary agent is selected from NSC 5284, diisopropyl phosphate, phosphorous
The mixture of one or more in acid tributyl, dibutyl phosphite, dibutylphosphoric acid ester, dimethylformamide.
The preparation method of 1,1,1,3,3-pentachloropropane the most according to claim 1, it is characterised in that in step (1)
Described vinyl chloride and carbon tetrachloride mol ratio are 1:3～5, and described catalyst amount is the 1～5% of vinyl chloride weight, reaction
Temperature is 80～120 DEG C, and reaction time is 0.5～2.0h.
The preparation method of 1,1,1,3,3-pentachloropropane the most according to claim 1, it is characterised in that in step (2)
The first described tower bottom of rectifying tower temperature is 90～115 DEG C, and pressure is-0.088～-0.095MPa.
The preparation method of 1,1,1,3,3-pentachloropropane the most according to claim 1, it is characterised in that in step (4)
Described Second distillation column bottom temperature is 45～70 DEG C, and pressure is-0.085～-0.099MPa.
The preparation method of 1,1,1,3,3-pentachloropropane the most according to claim 1, it is characterised in that described second
Rectifying column is molecular distillation tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610247011.9A CN105859512B (en) | 2016-04-19 | 2016-04-19 | Preparation method of 1,1,1,3, 3-pentachloropropane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610247011.9A CN105859512B (en) | 2016-04-19 | 2016-04-19 | Preparation method of 1,1,1,3, 3-pentachloropropane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105859512A true CN105859512A (en) | 2016-08-17 |
| CN105859512B CN105859512B (en) | 2019-01-22 |
Family
ID=56632888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610247011.9A Active CN105859512B (en) | 2016-04-19 | 2016-04-19 | Preparation method of 1,1,1,3, 3-pentachloropropane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105859512B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659322A (en) * | 2019-03-06 | 2020-09-15 | 浙江佳汇新材料有限公司 | Device and process for preparing 1,1,1, 3-tetrachloropropane |
| CN112427048A (en) * | 2020-12-15 | 2021-03-02 | 江苏景宏新材料科技有限公司 | Stannous salt complex catalyst and method for producing L-lactide by using same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086545A (en) * | 1998-09-18 | 2000-03-28 | Asahi Glass Co Ltd | Production of 1,1,1,3,3-pentachloropropane |
| US6313360B1 (en) * | 2000-09-29 | 2001-11-06 | Vulcan Materials Company | Process for the manufacture of 1, 1, 1, 3, 3-pentachloropropane |
| CN1958541A (en) * | 2006-11-17 | 2007-05-09 | 浙江蓝天环保高科技股份有限公司 | Method for preparing 1,1,1,3,3 - pentachlorobutane from materials of chloropropene and carbon tetrachloride under tempering and polymerizing catalyst |
| CN101913980A (en) * | 2010-09-07 | 2010-12-15 | 西安近代化学研究所 | Production method of 1,1,1,3,3-pentachloropropane |
| CN104513127A (en) * | 2014-11-28 | 2015-04-15 | 巨化集团技术中心 | 1,1,1,3,3-pentachloropropane preparation method |
-
2016
- 2016-04-19 CN CN201610247011.9A patent/CN105859512B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086545A (en) * | 1998-09-18 | 2000-03-28 | Asahi Glass Co Ltd | Production of 1,1,1,3,3-pentachloropropane |
| US6313360B1 (en) * | 2000-09-29 | 2001-11-06 | Vulcan Materials Company | Process for the manufacture of 1, 1, 1, 3, 3-pentachloropropane |
| CN1958541A (en) * | 2006-11-17 | 2007-05-09 | 浙江蓝天环保高科技股份有限公司 | Method for preparing 1,1,1,3,3 - pentachlorobutane from materials of chloropropene and carbon tetrachloride under tempering and polymerizing catalyst |
| CN101913980A (en) * | 2010-09-07 | 2010-12-15 | 西安近代化学研究所 | Production method of 1,1,1,3,3-pentachloropropane |
| CN104513127A (en) * | 2014-11-28 | 2015-04-15 | 巨化集团技术中心 | 1,1,1,3,3-pentachloropropane preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 刘毓林等: "1,1,1,3,3-五氯丙烷的连续制备", 《有机氟工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659322A (en) * | 2019-03-06 | 2020-09-15 | 浙江佳汇新材料有限公司 | Device and process for preparing 1,1,1, 3-tetrachloropropane |
| CN112427048A (en) * | 2020-12-15 | 2021-03-02 | 江苏景宏新材料科技有限公司 | Stannous salt complex catalyst and method for producing L-lactide by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105859512B (en) | 2019-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101395108B (en) | Method for producing fluorinated organic compounds | |
| CN104981449B (en) | For the method producing propylene dichloride | |
| JP5439177B2 (en) | Method for separating fluoroolefins from hydrogen fluoride by azeotropic distillation | |
| JP5953317B2 (en) | Method for producing 2,3,3,3-tetrafluoro-2-propene | |
| JP5732062B2 (en) | Integrated method for producing fluoroolefins | |
| CN103702931B (en) | The method separated and collect 2,3,3,3 tetrafluoropropenes and Fluohydric acid. | |
| CN102282114B (en) | Isomerization of 1,1,3,3-tetrafluoropropene | |
| JP6084168B2 (en) | For producing trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoropropane together Integration method | |
| JP6935423B2 (en) | Method for manufacturing 2,3,3,3-tetrafluoropropene | |
| CN107011113A (en) | The integrated approach of Joint Production trifluoro propene, tetrafluoropropene and pentafluoropropane | |
| EP1838649A2 (en) | Halocarbon production processes, halocarbon separation processes, and halocarbon production systems | |
| EP2826766B1 (en) | Production method for 2,3,3,3-tetra-fluoropropene | |
| CN105026348A (en) | Process for the production of chlorinated alkanes | |
| CN103189339A (en) | Continuous low-temperature process to produce trans-1-chloro-3,3,3-trifluoropropene | |
| JP2015515464A (en) | Integration to co-produce trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane process | |
| JP6908596B2 (en) | Method for producing C3 chlorinated alkane and alkene compound | |
| CN109438170B (en) | Preparation method of 2,3,3, 3-tetrafluoropropene | |
| CN102164882A (en) | Process for preparing 2,3,3,3-tetrafluoropropene | |
| CN105358233A (en) | Method of separating organofluorine compounds using membrane | |
| CN104710274B (en) | Process for co-producing 1,3,3,3-tetrafluoropropene and/or 2,3,3,3-tetrafluoropropene | |
| CN108473853A (en) | The method for preparing 2,3,3,3- tetrafluoropropenes and/or vinylidene fluoride | |
| CN105859512A (en) | Preparation method of 1,1,1,3, 3-pentachloropropane | |
| ES2755791T3 (en) | Preparation procedure for the joint production of HFO-1234ze and HFC-245fa | |
| CN106946647B (en) | A kind of method that the isomerization of mixture room temperature prepares trans-1,3,3,3-tetrafluoropropene | |
| JP2019531358A (en) | Simultaneous production method of low carbon foaming agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220509 Address after: 324004 Juhua Group, Quzhou City, Zhejiang Province Patentee after: ZHEJIANG QUHUA FLUOR-CHEMISTRY Co.,Ltd. Address before: 324004 No. 60, Beier Road, Kecheng District, Quzhou City, Zhejiang Province Patentee before: ZHEJIANG QUZHOU JUXIN FLUORINE CHEMICAL Co.,Ltd. Patentee before: ZHEJIANG QUHUA FLUOR-CHEMISTRY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231008 Address after: 324004 Juhua Group, Quzhou City, Zhejiang Province Patentee after: ZHEJIANG QUHUA FLUOR-CHEMISTRY Co.,Ltd. Patentee after: ZHEJIANG ENGINEERING DESIGN Co.,Ltd. Address before: 324004 Juhua Group, Quzhou City, Zhejiang Province Patentee before: ZHEJIANG QUHUA FLUOR-CHEMISTRY Co.,Ltd. |
|
| TR01 | Transfer of patent right |