CN106380371B - A kind of method of chlorofluorocarbons resource utilization - Google Patents
A kind of method of chlorofluorocarbons resource utilization Download PDFInfo
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- CN106380371B CN106380371B CN201610682344.4A CN201610682344A CN106380371B CN 106380371 B CN106380371 B CN 106380371B CN 201610682344 A CN201610682344 A CN 201610682344A CN 106380371 B CN106380371 B CN 106380371B
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 98
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims abstract description 15
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960003132 halothane Drugs 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 85
- 239000008246 gaseous mixture Substances 0.000 claims description 57
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 39
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 39
- 239000002585 base Substances 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 239000000376 reactant Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical group FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims description 5
- 229940051271 1,1-difluoroethane Drugs 0.000 claims description 4
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 39
- 239000001257 hydrogen Substances 0.000 abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 24
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical class CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 13
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 abstract description 10
- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical compound FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- LZFMACRHJXVTIV-UHFFFAOYSA-N [F].C(=C)Cl Chemical compound [F].C(=C)Cl LZFMACRHJXVTIV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 238000003682 fluorination reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 90
- 229910052757 nitrogen Inorganic materials 0.000 description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 37
- 238000010792 warming Methods 0.000 description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 18
- 230000004913 activation Effects 0.000 description 18
- 238000004587 chromatography analysis Methods 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 18
- 238000010926 purge Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 17
- 238000001035 drying Methods 0.000 description 12
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 10
- 239000011651 chromium Substances 0.000 description 8
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VEZJSKSPVQQGIS-UHFFFAOYSA-N 1-chloro-2-fluoroethane Chemical class FCCCl VEZJSKSPVQQGIS-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KBEZIROSXSGDKV-UHFFFAOYSA-N [Cl].CCF Chemical compound [Cl].CCF KBEZIROSXSGDKV-UHFFFAOYSA-N 0.000 description 3
- 238000004378 air conditioning Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 description 2
- 229910019589 Cr—Fe Inorganic materials 0.000 description 2
- AFLIPEBFYDIRNJ-UHFFFAOYSA-N FC(F)=C(F)[Zn] Chemical compound FC(F)=C(F)[Zn] AFLIPEBFYDIRNJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005796 dehydrofluorination reaction Methods 0.000 description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical group CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- UREJNEBJDURREH-UHFFFAOYSA-N 1,2-dibromo-1,1,2-trifluoroethane Chemical compound FC(Br)C(F)(F)Br UREJNEBJDURREH-UHFFFAOYSA-N 0.000 description 1
- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 description 1
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- -1 alkene separation Chemical compound 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007269 dehydrobromination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FQFKTKUFHWNTBN-UHFFFAOYSA-N trifluoro-$l^{3}-bromane Chemical compound FBr(F)F FQFKTKUFHWNTBN-UHFFFAOYSA-N 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
- C07C17/25—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
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of methods of chlorofluorocarbons resource utilization.Using halothane as raw material, under the conditions of different catalysts, certain temperature and material are than preparing hydrofluoroether through fluorination after reacting under control with alcohols.Simultaneously can also be under the conditions of different catalysts, certain temperature and material are than reacting two chlorofluoroethanes of preparation or Difluoroethane with hydrogen under control.The present invention develops downstream product for chlorofluoro-alkane and provides new method and thinking, not only avoid the safety and technological problems of the separation of the fluorine vinyl chloride such as trifluoro-ethylene and difluoro vinyl chloride, using addition or add the reaction such as hydrogen simultaneously, generating has certain market and with more products such as two chlorofluoroethanes of economic value, hydrofluoroethers, has potential utility value and huge industrial applications meaning.This method can effectively extend catalyst service life, be effectively utilized such as difluoro vinyl chloride intermediate product, be simple and efficient.
Description
Technical field
The present invention relates to a kind of methods of chlorofluorocarbons resource utilization, belong to pernicious gas recycling and recycle field.
Background technique
As climate change especially global warming issue becomes increasingly conspicuous, international community was to high GWP value in recent years
The use of HFCs is limited, and is formulated and be endorsed corresponding laws and regulations and carry out eliminating gradually.It was signed in 1997 various countries
Kyoto Protocol has been affixed one's name to, HFCs is defined as to one of greenhouse gases controlled in 6.Under this situation, various countries propose phase respectively
The regulation and motion answered, it is intended to gradually limit production, consumption and the foreign trade of HFCs.1,1,1,2- tetrafluoroethane, 1,1,
1- trifluoroethane etc. is affected to global warming because the latent value (GWP) of its greenhouse effects is higher, therefore is listed in time limit and washes in a pan
Eliminate kind.Wherein European Union forbade the air-conditioning of all new production automobiles to be higher than 150 system using GWP value from January 1st, 2017
Cryogen；Splitting air conditioner is forbidden to use the refrigerant that GWP value is higher than 150 from January 1st, 2015.The U.S. 2021
The air-conditioning of new production automobile is forbidden to use R134a afterwards.Japan's air-conditioning of new production automobile from 2023 is forbidden to use GWP value height
In 150 refrigerant.From the point of view of the above various countries treat HFCs, HFCs product is gradually eliminated will be imperative.Similar 1,1,1,
2- tetrafluoroethane, 1, the Related products such as 1,1- trifluoroethane also will gradually reduce in related fields, or even in certain application aspects
It is substituted completely.Therefore, the resource utilization of fluorochloroparaffins need to be accelerated to study, and can gradually form down after substitution starts as early as possible
Swim product.
103288589 A of CN discloses a kind of method for producing trifluoro-ethylene coproduction hydrogen fluoride, with 1,1,1,2- tetrafluoro second
Alkane is primary raw material, produces trifluoro-ethylene by dehydrofluorination.The invention is that 1,1,1,2- tetrafluoroethane is converted to trifluoro second
Alkene, but trifluoro-ethylene height is inflammable, is easy autohemagglutination, is not easy storage and transport, therefore above provide HFA 134a
For the method that source utilizes there are safety problem in industrial application, industrialized production difficulty is larger.
104844411 A of CN discloses a kind of synthesis hexafluoro -1,3-butadiene method, with HFA 134a
For raw material, dehydrofluorination generates trifluoro-ethylene under the action of catalyst, then trifluoro-ethylene and bromine in another reactor
Reaction generates 1,2- bis- bromo- 1,1,2- trifluoroethane, then dehydrobromination obtains bromotrifluoroethylene, trifluoro bromine second under alkaline condition
Alkene is reacted with activated zinc powder, n,N-Dimethylformamide generates trifluoro vinyl zinc, and trifluoro vinyl zinc is in Fe3+Under the action of send out
Raw coupling reaction generates hexafluoro-1,3-butadiene.This method is although it is contemplated that the safety problem of trifluoro-ethylene, by the first step
Reaction product rapidly enters in second reactor, is reacted with bromine, reduces risk to a certain extent, but still exist
Trifluoro-ethylene shifts to an earlier date the possibility of autohemagglutination, and subsequent processes are complex, and bromine is also a kind of chemicals of highly dangerous,
It is equally unfavorable to use industrial applications.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of method of chlorofluorocarbons resource utilization.
Gas phase reaction is carried out using chlorine fluoroethane and alcohols or hydrogen, prepares hydrofluoroether class or two chlorofluoroethanes and difluoro second
Alkane.The method of resource utilization provided by the invention efficiently uses fluorochloroparaffins, not only avoids trifluoro-ethylene and difluoro chloroethene
The safety and technological problems of the fluorine vinyl chloride such as alkene separation, while using addition or adding the reaction such as hydrogen, generate have certain market and
With more products such as two chlorofluoroethanes of economic value, hydrofluoroethers.
Technical scheme is as follows:
The method of chlorofluorocarbons resource utilization, the method include two aspect resource utilizations, and a kind of direction is and alcohols system
Standby hydrofluoroether, another direction are that two chlorofluoroethanes of preparation and Difluoroethane are reacted with hydrogen.
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) it after alcohol gasifying, is mixed with halothane, is reacted under catalyst A effect, obtain reactant；
(2) reactant that step (1) obtains is mixed with hydrogen fluoride gas, reacts, must mixes under catalyst B effect
Gas；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Preferred according to the present invention, halothane is fluoroethane or chlorine fluoroethane in the step (1).
It is further preferred that the halothane be HFA 134a, 1,1,1- trifluoro-2-chloroethane, 1,1,
1- trifluoroethane, the fluoro- 2- chloroethanes of 1,1- bis- or 1,1- Difluoroethane.
It is further preferred that the halothane is HFA 134a or 1,1,1- trifluoro-2-chloroethane.
Preferred according to the present invention, catalyst A is chromium base or aluminium base gas phase catalyst in the step (1).
It is further preferred that the catalyst is Cr, Cr-Al, Cr-Mg, Cr-Cu or Cr-Fe base gas phase catalyst.
Preferred according to the present invention, catalyst B is metal fluoride base gas phase catalyst in the step (2).
It is further preferred that the catalyst B is NaF, KF, NaF/Al2O3、CrF3/Al2O3。
Preferred according to the present invention, the catalyst A, catalyst B are at 300 DEG C, hydrogen fluoride gas and inert gas atmosphere
Under enclosing, it is activated.
It is further preferred that the volume ratio of the inert gas and hydrogen fluoride gas is 2-5:1.
Preferred according to the present invention, the alcohol in the step (1) is fluorine-containing alcohol.
Preferred according to the present invention, the alcohol in the step (1) is methanol, dimethanol, ethyl alcohol or trifluoroethanol, propyl alcohol.
Preferred according to the present invention, alcohol and halothane mixed volume ratio are 1:0.1-1:10 in the step (1).
Preferred according to the present invention, reaction temperature is 300-550 DEG C in the step (1), reaction pressure 0.1-
0.5Mpa, reaction time 2h.
It is further preferred that reaction temperature is 350-500 DEG C in the step (1), reaction pressure 0.15-0.3Mpa.
Preferred according to the present invention, reaction temperature is 200-500 DEG C in the step (2), and reaction pressure is normal pressure, reaction
Time is 2h.
It is further preferred that reaction temperature is 200-350 DEG C in the step (2).
Preferred according to the present invention, the volume ratio of reactant and hydrogen fluoride gas is 1:0.1-1:10 in the step (2).
The reaction mainly utilizes chlorofluorocarbons to eliminate and generates chlorine fluoroolefins, then after carrying out addition with alcohols, with the fluorine such as hydrogen fluoride
Change reagent to be fluorinated, obtains reaction product.
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) halothane reacts under catalyst C effect, obtains reactant；
(2) reactant that step (1) obtains is mixed with hydrogen, is reacted under catalyst D effect, obtains gaseous mixture；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Preferred according to the present invention, the catalyst C in the step (1) is chromium base or aluminium base gas phase catalyst.
It is further preferred that the catalyst C is Cr, Cr-Al, Cr-Mg, Cr-Cu or Cr-Fe base gas phase catalyst.
Preferred according to the present invention, the catalyst D in the step (2) is noble metal-based catalysts.
It is further preferred that the catalyst D is Pd/C, Pd/Al2O3、Ni/Al2O3、Ni-Cr/Al2O3。
Preferred according to the present invention, catalyst C in the step (1) is at 300 DEG C, hydrogen fluoride gas and inert gas
Under atmosphere, it is activated；Catalyst D in the step (2) is activated at 300 DEG C, under atmosphere of hydrogen.
It is further preferred that the volume ratio of the inert gas and hydrogen fluoride gas is 2-5:1.
Preferred according to the present invention, halothane is fluoroethane or chlorine fluoroethane in the step (1).
It is further preferred that the halothane be HFA 134a, 1,1,1- trifluoro-2-chloroethane, 1,1,
1- trifluoroethane, the fluoro- 2- chloroethanes of 1,1- bis- or 1,1- Difluoroethane.
It is further preferred that the halothane is HFA 134a or 1,1,1- trifluoro-2-chloroethane.
Preferred according to the present invention, reaction temperature is 350-600 DEG C in the step (1), reaction pressure 0.1-
0.5Mpa, reaction time 2h.
It is further preferred that reaction temperature is 450-500 DEG C in the step (1), reaction pressure 0.15-0.3Mpa.
Preferred according to the present invention, reaction temperature is 100-350 DEG C in the step (2), reaction pressure 0.1-
0.5Mpa, air speed 300-1000h-1, reaction time 2h.
It is further preferred that reaction temperature is 150-200 DEG C, reaction pressure 0.2-0.4Mpa in the step (2), it is empty
Speed is 500-800h-1。
Preferred according to the present invention, the volume ratio of reactant and hydrogen is 1-4:1 in the step (2).
The reaction mainly utilizes chlorofluorocarbons to eliminate and generates perhaloalkenes, then with after hydrogen progress addition and substitution reaction, obtains
To reaction products such as corresponding fluorine-containing alkane.
Beneficial effects of the present invention are as follows:
The present invention passes through using the chlorofluoro-alkane of high GWP value and high ODP value as raw material, is produced downstream by reacting preparation
Product, not only avoid the safety and technological problems of the separation of the fluorine vinyl chloride such as trifluoro-ethylene and difluoro vinyl chloride, while utilizing addition
Or add the reaction such as hydrogen, generating has certain market and with more products such as two chlorofluoroethanes of economic value, hydrofluoroethers.Especially
International community substitutes fluorochloroparaffins product in popularity novel refrigerant HFO-1234yf etc., and the present invention is developed to fluorochloroparaffins
Downstream product provides new method and thinking, has potential utility value.
This method can effectively extend catalyst service life, be effectively utilized such as difluoro vinyl chloride intermediate product, letter
It is single efficient.
Specific embodiment
The present invention is described further combined with specific embodiments below, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The reagent and material
Material, unless otherwise specified, commercially obtains.
The preparation of catalyst A: 100g chromium chloride is dissolved in 1L water, and 3.6g Al (NO is added thereto3)3It is hybridly prepared into
Mixing salt solution, then ammonium hydroxide is added into mixing salt solution and is reacted, it adjusts pH value in reaction and is maintained between 8.5-10, not
It is sufficiently precipitated under conditions of disconnected stirring, using filter, drying, the mixing for obtaining the hydroxide of hydroxide and aluminium containing chromium is heavy
It forms sediment；Mixed precipitation is roasted at 600 DEG C, obtains the catalyst of the oxide containing chromium and aluminium, abbreviation Cr-Al base gas phase catalysis
Agent.
Embodiment 1
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst n aF in reactor 2；Reactor 1,2 under nitrogen protection, 120 DEG C of dryings
12 hours；Nitrogen and hydrogen fluoride gas are passed through reactor 1,2 according to the ratio of 2.5:1, reactor 1,2 is risen with 2-3 DEG C/minute
Warm rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；
Continue to keep nitrogen purging after the completion of activation, until content of fluoride ion is less than 0.3% in gaseous mixture；
(2) after dimethanol being gasified, and 1,1,1- trifluoro-2-chloroethane is mixed according to volume ratio 1:8, is passed through reactor 1
2h is reacted, controls 300 DEG C of reaction temperature, pressure 0.15Mpa；Material and hydrogen fluoride gas in reactor 1 is according to volume ratio 1:5
Mixing is passed through reactor 2 and reacts 2h, controls 200 DEG C of reaction temperature, pressure normal pressure is reacted, and gaseous mixture is obtained；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Carry out gas chromatographic analysis, hydrofluoroether content 20% in product.
Embodiment 2
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst KF in reactor 2；Reactor 1,2 under nitrogen protection, 120 DEG C of dryings 12
Hour；Nitrogen and hydrogen fluoride gas are passed through reactor 1,2 according to the ratio of 2.5:1, reactor 1,2 is heated up with 2-3 DEG C/minute
Rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；
Continue to keep nitrogen purging after the completion of activation, until content of fluoride ion is less than 0.3% in gaseous mixture；
(2) by after methyl alcohol vaporizing, and 1,1,1- trifluoro-2-chloroethane is mixed according to volume ratio 1:8, and it is anti-to be passed through reactor 1
2h is answered, controls 400 DEG C of reaction temperature, pressure 0.15Mpa；Material and hydrogen fluoride gas in reactor 1 is mixed according to volume ratio 1:5
Conjunction is passed through reactor 2 and reacts 2h, controls 200 DEG C of reaction temperature, pressure normal pressure is reacted, and gaseous mixture is obtained；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Carry out gas chromatographic analysis, hydrofluoroether content 40% in product.
Embodiment 3
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst n aF/Al in reactor 22O3；Reactor 1,2 under nitrogen protection, 120 DEG C
It is 12 hours dry；Nitrogen and hydrogen fluoride gas are passed through reactor 1,2 according to the ratio of 2.5:1, by reactor 1,2 with 2-3 DEG C/
Point heating rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；
Continue to keep nitrogen purging after the completion of activation, until content of fluoride ion is less than 0.3% in gaseous mixture；
(2) after dimethanol being vaporized, and 1,1,1- trifluoro-2-chloroethane is mixed according to volume ratio 1:8, is passed through reactor 1
2h is reacted, controls 300 DEG C of reaction temperature, pressure 0.15Mpa；Material and hydrogen fluoride gas in reactor 1 is according to volume ratio 1:5
Mixing is passed through reactor 2 and reacts 2h, controls 300 DEG C of reaction temperature, pressure normal pressure is reacted, and gaseous mixture is obtained；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Carry out gas chromatographic analysis, hydrofluoroether content 43% in product.
Embodiment 4
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst CrF in reactor 23/Al2O3；Reactor 1,2 under nitrogen protection, 120
DEG C dry 12 hours；Nitrogen and hydrogen fluoride gas are passed through reactor 1,2 according to the ratio of 2.5:1, by reactor 1,2 with 2-3
DEG C/minute heating rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；
Continue to keep nitrogen purging after the completion of activation, until content of fluoride ion is less than 0.3% in gaseous mixture；
(2) after will be ethanol evaporating, and 1,1,1- trifluoroethane is mixed according to volume ratio 1:0.1, is passed through the reaction of reactor 1
2h controls 400 DEG C of reaction temperature, pressure 0.3Mpa；Material in reactor 1 is mixed with hydrogen fluoride gas according to volume ratio 1:5
It is passed through reactor 2 and reacts 2h, control 300 DEG C of reaction temperature, pressure normal pressure is reacted, and gaseous mixture is obtained；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Carry out gas chromatographic analysis, hydrofluoroether content 57% in product.
Embodiment 5
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst n aF/Al in reactor 22O3；Reactor 1,2 under nitrogen protection, 120 DEG C
It is 12 hours dry；Nitrogen and hydrogen fluoride gas are passed through reactor 1,2 according to the ratio of 2.5:1, by reactor 1,2 with 2-3 DEG C/
Point heating rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；
Continue to keep nitrogen purging after the completion of activation, until content of fluoride ion is less than 0.3% in gaseous mixture；
(2) it after vaporizing trifluoroethanol, is mixed with 1,1- Difluoroethane according to volume ratio 1:10, is passed through the reaction of reactor 1
2h controls 300 DEG C of reaction temperature, pressure 0.2Mpa；Material in reactor 1 is mixed with hydrogen fluoride gas according to volume ratio 1:5
It is passed through reactor 2 and reacts 2h, control 200 DEG C of reaction temperature, pressure normal pressure is reacted, and gaseous mixture is obtained；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Carry out gas chromatographic analysis, hydrofluoroether content 23% in product.
Embodiment 6
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst n aF/Al in reactor 22O3；Reactor 1,2 under nitrogen protection, 120 DEG C
It is 12 hours dry；Nitrogen and hydrogen fluoride gas are passed through reactor 1,2 according to the ratio of 2:1, by reactor 1,2 with 2-3 DEG C/minute
Heating rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；
Continue to keep nitrogen purging after the completion of activation, until content of fluoride ion is less than 0.3% in gaseous mixture；
(2) after dimethanol being vaporized, and 1,1,1- trifluoro-2-chloroethane is mixed according to volume ratio 1:5, is passed through reactor 1
2h is reacted, controls 500 DEG C of reaction temperature, pressure 0.15Mpa；Material and hydrogen fluoride gas in reactor 1 is according to volume ratio 1:5
Mixing is passed through reactor 2 and reacts 2h, controls 200 DEG C of reaction temperature, pressure normal pressure is reacted, and gaseous mixture is obtained；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Carry out gas chromatographic analysis, hydrofluoroether content 38% in product.
Embodiment 7
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst n aF/Al in reactor 22O3；Reactor 1,2 under nitrogen protection, 120 DEG C
It is 12 hours dry；Nitrogen and hydrogen fluoride gas are passed through reactor 1,2 according to the ratio of 5:1, by reactor 1,2 with 2-3 DEG C/minute
Heating rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；
Continue to keep nitrogen purging after the completion of activation, until content of fluoride ion is less than 0.3% in gaseous mixture；
(2) it after vaporizing dimethanol, is mixed with the fluoro- 2- chloroethanes of 1,1- bis- according to volume ratio 1:3, it is anti-to be passed through reactor 1
2h is answered, controls 300 DEG C of reaction temperature, pressure 0.1Mpa；Material and hydrogen fluoride gas in reactor 1 is according to volume ratio 1:0.1
Mixing is passed through reactor 2 and reacts 2h, controls 350 DEG C of reaction temperature, pressure normal pressure is reacted, and gaseous mixture is obtained；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Carry out gas chromatographic analysis, hydrofluoroether content 34% in product.
Embodiment 8
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst n aF/Al in reactor 22O3；Reactor 1,2 under nitrogen protection, 120 DEG C
It is 12 hours dry；Nitrogen and hydrogen fluoride gas are passed through reactor 1,2 according to the ratio of 2.5:1, by reactor 1,2 with 2-3 DEG C/
Point heating rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；
Continue to keep nitrogen purging after the completion of activation, until content of fluoride ion is less than 0.3% in gaseous mixture；
(2) after dimethanol being vaporized, and 1,1,1- trifluoro-2-chloroethane is mixed according to volume ratio 1:5, is passed through reactor 1
2h is reacted, controls 350 DEG C of reaction temperature, pressure 0.15Mpa；Material and hydrogen fluoride gas in reactor 1 is according to volume ratio 1:3
Mixing is passed through reactor 2 and reacts 2h, controls 200 DEG C of reaction temperature, pressure normal pressure is reacted, and gaseous mixture is obtained；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Carry out gas chromatographic analysis, hydrofluoroether content 42% in product.
Embodiment 9
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst n aF/Al in reactor 22O3；Reactor 1,2 under nitrogen protection, 120 DEG C
It is 12 hours dry；Nitrogen and hydrogen fluoride gas are passed through reactor 1,2 according to the ratio of 2.5:1, by reactor 1,2 with 2-3 DEG C/
Point heating rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；
Continue to keep nitrogen purging after the completion of activation, until content of fluoride ion is less than 0.3% in gaseous mixture；
(2) it after vaporizing dimethanol, is mixed with HFA 134a according to volume ratio 1:8, is passed through the reaction of reactor 1
2h controls 550 DEG C of reaction temperature, pressure 0.5Mpa；Material in reactor 1 is mixed with hydrogen fluoride gas according to volume ratio 1:10
It is passed through reactor 2 and reacts 2h, control 500 DEG C of reaction temperature, pressure normal pressure is reacted, and gaseous mixture is obtained；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
Carry out gas chromatographic analysis, hydrofluoroether content 27% in product.
Embodiment 10
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst Pd/C in reactor 2；Under nitrogen protection, 120 DEG C drying 12 hours；
(2) nitrogen and hydrogen fluoride gas are passed through reactor 1 according to the ratio of 2.5:1, reactor 1 is risen with 2-3 DEG C/minute
Warm rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；Continue to keep inert gas purge after the completion of activation, until
Content of fluoride ion is less than 0.3% in gaseous mixture；
Hydrogen is passed through in reactor 2, is warming up to 300 DEG C with 1-2 DEG C/minute, pre-activate processing is carried out to catalyst Pd/C
12 hours.
(3) by 0.2L1,1,1- trifluoro-2-chloroethane, which is passed through in reactor 1, reacts 2h, controls 400 DEG C of reaction temperature, pressure
Power 0.2Mpa；Reactant in reactor 1 is passed through reactor 2 according to volume ratio 1:1 mixing with hydrogen and reacts 2h, control reaction
120 DEG C of temperature, pressure 0.25Mpa, air speed 600h-1, obtain gaseous mixture；
(4) gaseous mixture that step (3) obtains is obtained into product through washing, alkali cleaning.
Gas chromatographic analysis is carried out, wherein two chlorofluoroethane contents 35%, Difluoroethane content 50%.
Embodiment 11
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst Pd/Al in reactor 22O3；Under nitrogen protection, 120 DEG C of dryings 12 are small
When；
(2) nitrogen and hydrogen fluoride gas are passed through reactor 1 according to the ratio of 2.5:1, reactor 1 is risen with 2-3 DEG C/minute
Warm rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；Continue to keep inert gas purge after the completion of activation, until
Content of fluoride ion is less than 0.3% in gaseous mixture；
Hydrogen is passed through in reactor 2,300 DEG C are warming up to 1-2 DEG C/minute, to catalyst Pd/Al2O3It carries out at pre-activate
Reason 12 hours.
(3) by 0.2L1,1,1,2- tetrafluoroethane, which is passed through in reactor 1, reacts 2h, controls 470 DEG C of reaction temperature, pressure
0.2Mpa；Reactant in reactor 1 is passed through reactor 2 according to volume ratio 1:1 mixing with hydrogen and reacts 2h, control reaction temperature
120 DEG C, pressure 0.2Mpa, air speed 500h of degree-1, obtain gaseous mixture；
(4) gaseous mixture that step (3) obtains is obtained into product through washing, alkali cleaning.
Gas chromatographic analysis is carried out, wherein two chlorofluoroethane contents 45%, Difluoroethane content 40%.
Embodiment 12
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst n i/Al in reactor 22O3；Under nitrogen protection, 120 DEG C of dryings 12 are small
When；
(2) nitrogen and hydrogen fluoride gas are passed through reactor 1 according to the ratio of 2.5:1, reactor 1 is risen with 2-3 DEG C/minute
Warm rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；Continue to keep inert gas purge after the completion of activation, until
Content of fluoride ion is less than 0.3% in gaseous mixture；
Hydrogen is passed through in reactor 2,300 DEG C are warming up to 1-2 DEG C/minute, to catalyst n i/Al2O3It carries out at pre-activate
Reason 12 hours.
(3) by 0.2L1,1,1- trifluoroethane, which is passed through in reactor 1, reacts 2h, controls 400 DEG C of reaction temperature, pressure
0.2Mpa；Reactant in reactor 1 is passed through reactor 2 according to volume ratio 2:1 mixing with hydrogen and reacts 2h, control reaction temperature
170 DEG C, pressure 0.25Mpa, air speed 600h of degree-1, obtain gaseous mixture；
(4) gaseous mixture that step (3) obtains is obtained into product through washing, alkali cleaning.
Gas chromatographic analysis is carried out, wherein two chlorofluoroethane contents 17%, Difluoroethane content 65%.
Embodiment 13
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst n i-Cr/Al in reactor 22O3；Under nitrogen protection, 120 DEG C of dryings 12
Hour；
(2) nitrogen and hydrogen fluoride gas are passed through reactor 1 according to the ratio of 2.5:1, reactor 1 is risen with 2-3 DEG C/minute
Warm rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；Continue to keep inert gas purge after the completion of activation, until
Content of fluoride ion is less than 0.3% in gaseous mixture；
Hydrogen is passed through in reactor 2,300 DEG C are warming up to 1-2 DEG C/minute, to catalyst n i-Cr/Al2O3Carry out pre- work
Change processing 12 hours.
(3) by 0.2L1, the fluoro- 2- chloroethanes of 1- bis-, which is passed through in reactor 1, reacts 2h, controls 470 DEG C of reaction temperature, pressure
0.2Mpa；Reactant in reactor 1 is passed through reactor 2 according to volume ratio 2:1 mixing with hydrogen and reacts 2h, control reaction temperature
170 DEG C, pressure 0.4Mpa, air speed 800h of degree-1, obtain gaseous mixture；
(4) gaseous mixture that step (3) obtains is obtained into product through washing, alkali cleaning.
Gas chromatographic analysis is carried out, wherein two chlorofluoroethane contents 22%, Difluoroethane content 60%.
Embodiment 14
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst Pd/Al in reactor 22O3；Under nitrogen protection, 120 DEG C of dryings 12 are small
When；
(2) nitrogen and hydrogen fluoride gas are passed through reactor 1 according to the ratio of 2.5:1, reactor 1 is risen with 2-3 DEG C/minute
Warm rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；Continue to keep inert gas purge after the completion of activation, until
Content of fluoride ion is less than 0.3% in gaseous mixture；
Hydrogen is passed through in reactor 2,300 DEG C are warming up to 1-2 DEG C/minute, to catalyst Pd/Al2O3It carries out at pre-activate
Reason 12 hours.
(3) by 0.2L1,1,1- trifluoro-2-chloroethane, which is passed through in reactor 1, reacts 2h, controls 450 DEG C of reaction temperature, pressure
Power 0.3Mpa；Reactant in reactor 1 is passed through reactor 2 according to volume ratio 2:1 mixing with hydrogen and reacts 2h, control reaction
150 DEG C of temperature, pressure 0.3Mpa, air speed 600h-1, obtain gaseous mixture；
(4) gaseous mixture that step (3) obtains is obtained into product through washing, alkali cleaning.
Gas chromatographic analysis is carried out, wherein two chlorofluoroethane contents 18%, Difluoroethane content 63%.
Embodiment 15
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst Pd/Al in reactor 22O3；Under nitrogen protection, 120 DEG C of dryings 12 are small
When；
(2) nitrogen and hydrogen fluoride gas are passed through reactor 1 according to the ratio of 2.5:1, reactor 1 is risen with 2-3 DEG C/minute
Warm rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；Continue to keep inert gas purge after the completion of activation, until
Content of fluoride ion is less than 0.3% in gaseous mixture；
Hydrogen is passed through in reactor 2,300 DEG C are warming up to 1-2 DEG C/minute, to catalyst Pd/Al2O3It carries out at pre-activate
Reason 12 hours.
(3) by 0.2L1,1,1- trifluoro-2-chloroethane, which is passed through in reactor 1, reacts 2h, controls 400 DEG C of reaction temperature, pressure
Power 0.15Mpa；Reactant in reactor 1 is passed through reactor 2 according to volume ratio 2:1 mixing with hydrogen and reacts 2h, control is anti-
120 DEG C of temperature are answered, pressure 0.25Mpa, air speed 800h-1, obtain gaseous mixture；
(4) gaseous mixture that step (3) obtains is obtained into product through washing, alkali cleaning.
Gas chromatographic analysis is carried out, wherein two chlorofluoroethane contents 27%, Difluoroethane content 54%.
Embodiment 16
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst Pd/C in reactor 2；Under nitrogen protection, 120 DEG C drying 12 hours；
(2) nitrogen and hydrogen fluoride gas are passed through reactor 1 according to the ratio of 2.5:1, reactor 1 is risen with 2-3 DEG C/minute
Warm rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；Continue to keep inert gas purge after the completion of activation, until
Content of fluoride ion is less than 0.3% in gaseous mixture；
Hydrogen is passed through in reactor 2, is warming up to 300 DEG C with 1-2 DEG C/minute, pre-activate processing is carried out to catalyst Pd/C
12 hours.
(3) by 0.2L1,1- Difluoroethane, which is passed through in reactor 1, reacts 2h, controls 500 DEG C of reaction temperature, pressure
0.2Mpa；Reactant in reactor 1 is passed through reactor 2 according to volume ratio 2:1 mixing with hydrogen and reacts 2h, control reaction temperature
200 DEG C, pressure 0.3Mpa, air speed 800h of degree-1, obtain gaseous mixture；
(4) gaseous mixture that step (3) obtains is obtained into product through washing, alkali cleaning.
Gas chromatographic analysis is carried out, wherein two chlorofluoroethane contents 24%, Difluoroethane content 58%.
Embodiment 17
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst Pd/C in reactor 2；Under nitrogen protection, 120 DEG C drying 12 hours；
(2) nitrogen and hydrogen fluoride gas are passed through reactor 1 according to the ratio of 2:1, reactor 1 is heated up with 2-3 DEG C/minute
Rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；Continue to keep inert gas purge after the completion of activation, until mixed
Content of fluoride ion is less than 0.3% in conjunction gas；
Hydrogen is passed through in reactor 2, is warming up to 300 DEG C with 1-2 DEG C/minute, pre-activate processing is carried out to catalyst Pd/C
12 hours.
(3) by 0.2L1,1- Difluoroethane, which is passed through in reactor 1, reacts 2h, controls 350 DEG C of reaction temperature, pressure
0.1Mpa；Reactant in reactor 1 is passed through reactor 2 according to volume ratio 2:1 mixing with hydrogen and reacts 2h, control reaction temperature
100 DEG C, pressure 0.1Mpa, air speed 300h of degree-1, obtain gaseous mixture；
(4) gaseous mixture that step (3) obtains is obtained into product through washing, alkali cleaning.
Gas chromatographic analysis is carried out, wherein two chlorofluoroethane contents 26%, Difluoroethane content 58%.
Embodiment 18
A kind of method of chlorofluorocarbons resource utilization, comprises the following steps that
(1) reactor 1,2 is the nickel tube for the Φ 46 × 3 that a root long is 1000mm, is packed into 100mlCr- in reactor 1
Al base gas phase catalyst is packed into 100ml catalyst Pd/C in reactor 2；Under nitrogen protection, 120 DEG C drying 12 hours；
(2) nitrogen and hydrogen fluoride gas are passed through reactor 1 according to the ratio of 5:1, reactor 1 is heated up with 2-3 DEG C/minute
Rate is warming up to 300 DEG C, is activated for 24 hours to catalyst；Continue to keep inert gas purge after the completion of activation, until mixed
Content of fluoride ion is less than 0.3% in conjunction gas；
Hydrogen is passed through in reactor 2, is warming up to 300 DEG C with 1-2 DEG C/minute, pre-activate processing is carried out to catalyst Pd/C
12 hours.
(3) by 0.2L1,1- Difluoroethane, which is passed through in reactor 1, reacts 2h, controls 600 DEG C of reaction temperature, pressure
0.5Mpa；Reactant in reactor 1 is passed through reactor 2 according to volume ratio 4:1 mixing with hydrogen and reacts 2h, control reaction temperature
350 DEG C, pressure 0.5Mpa, air speed 1000h of degree-1, obtain gaseous mixture；
(4) gaseous mixture that step (3) obtains is obtained into product through washing, alkali cleaning.
Gas chromatographic analysis is carried out, wherein two chlorofluoroethane contents 26%, Difluoroethane content 58%.
Claims (5)
1. a kind of method of chlorofluorocarbons resource utilization, which is characterized in that comprise the following steps that
(1) it after alcohol gasifying, is mixed with halothane, is reacted under catalyst A effect, obtain reactant；
The halothane is 1,1,1- trifluoro-2-chloroethane, 1,1,1- trifluoroethane or 1,1- Difluoroethane；The alcohol is first
Alcohol, ethyl alcohol or trifluoroethanol；The catalyst A is Cr-Al base gas phase catalyst；
(2) reactant that step (1) obtains is mixed with hydrogen fluoride gas, is reacted under catalyst B effect, obtains gaseous mixture；
The catalyst B is KF, NaF/Al2O3、CrF3/Al2O3；
(3) gaseous mixture that step (2) obtains is obtained into product through washing, alkali cleaning.
2. the method for chlorofluorocarbons resource utilization according to claim 1, which is characterized in that halogenated in the step (1)
Ethane is 1,1,1- trifluoro-2-chloroethane.
3. the method for chlorofluorocarbons resource utilization according to claim 1, which is characterized in that catalysis in the step (1)
Catalyst B is activated at 300 DEG C, under hydrogen fluoride gas and atmosphere of inert gases in agent A, step (2)；It is described lazy
Property gas and hydrogen fluoride gas volume ratio be 2-5:1.
4. the method for chlorofluorocarbons resource utilization according to claim 1, which is characterized in that in the step (1) alcohol with
Halothane mixed volume ratio is 1:0.1-1:10；The volume ratio of reactant and hydrogen fluoride gas is 1 in the step (2):
0.1-1:10。
5. the method for chlorofluorocarbons resource utilization according to claim 1, which is characterized in that reaction in the step (1)
Temperature is 300-550 DEG C, reaction pressure 0.1-0.5MPa, reaction time 2h；Reaction temperature is 200- in the step (2)
500 DEG C, reaction pressure is normal pressure, reaction time 2h.
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| US4504686A (en) * | 1982-08-16 | 1985-03-12 | Daikin Kogyo Co., Ltd. | Process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether |
| CN1651378A (en) * | 2004-12-27 | 2005-08-10 | 大连振邦氟涂料股份有限公司 | New hydrofluoro ether and its preparation method |
| CN104844411A (en) * | 2015-04-03 | 2015-08-19 | 北京宇极科技发展有限公司 | Method for synthesizing hexafluoro-1,3-butadiene |
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| GB9204072D0 (en) * | 1992-02-26 | 1992-04-08 | Ici Plc | Fluorination catalyst and process |
| JPH0687771A (en) * | 1992-09-04 | 1994-03-29 | Daikin Ind Ltd | Production of 1,1,1,2,3-pentafluoropropane |
| US5523498A (en) * | 1992-12-08 | 1996-06-04 | E. I. Du Pont De Nemours And Company | Process for reducing the fluorine content of hydrofluorocarbons and hydrohalofluorocarbons |
| CN101921172B (en) * | 2010-08-27 | 2013-04-10 | 中国科学院上海有机化学研究所 | Preparation of vinylidene fluoride from 1,1,1-trifluoro-chloroethane by liquid phase method |
| CA2967179A1 (en) * | 2014-12-11 | 2016-06-16 | Arkema France | Process for the preparation of 1-chloro-2,2-difluoroethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4504686A (en) * | 1982-08-16 | 1985-03-12 | Daikin Kogyo Co., Ltd. | Process for preparing 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether |
| CN1651378A (en) * | 2004-12-27 | 2005-08-10 | 大连振邦氟涂料股份有限公司 | New hydrofluoro ether and its preparation method |
| CN104844411A (en) * | 2015-04-03 | 2015-08-19 | 北京宇极科技发展有限公司 | Method for synthesizing hexafluoro-1,3-butadiene |
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| CN106380371A (en) | 2017-02-08 |
| CN109516895A (en) | 2019-03-26 |
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