CN116946978A - Method for preparing high-purity carbon tetrafluoride and chlorine - Google Patents
Method for preparing high-purity carbon tetrafluoride and chlorine Download PDFInfo
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- CN116946978A CN116946978A CN202311218253.1A CN202311218253A CN116946978A CN 116946978 A CN116946978 A CN 116946978A CN 202311218253 A CN202311218253 A CN 202311218253A CN 116946978 A CN116946978 A CN 116946978A
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- chlorine
- carbon tetrafluoride
- catalyst
- purity carbon
- gas
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000000460 chlorine Substances 0.000 title claims abstract description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 46
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011737 fluorine Substances 0.000 claims abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 15
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000003682 fluorination reaction Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000008188 pellet Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 159000000008 strontium salts Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 15
- 238000005580 one pot reaction Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 22
- 238000004817 gas chromatography Methods 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 239000007795 chemical reaction product Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000010926 purge Methods 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- IHNDUGMUECOVKK-UHFFFAOYSA-N aluminum chromium(3+) oxygen(2-) Chemical class [O-2].[Cr+3].[O-2].[Al+3] IHNDUGMUECOVKK-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 150000003841 chloride salts Chemical group 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 iron-chromium-aluminum Chemical compound 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NJCQVAKYBOCUCS-UHFFFAOYSA-N [C].F Chemical compound [C].F NJCQVAKYBOCUCS-UHFFFAOYSA-N 0.000 description 1
- PFNXDLYOYLRRNH-UHFFFAOYSA-N [C].FCl Chemical compound [C].FCl PFNXDLYOYLRRNH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005360 phosphosilicate glass Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
Abstract
The invention discloses a method for preparing high-purity carbon tetrafluoride and chlorine, and belongs to the technical field of carbon tetrafluoride. The technical proposal is as follows: taking carbon tetrachloride as a raw material, taking alkaline earth metal Sr modified alumina-chromium oxide as a catalyst, introducing fluorine-containing gas flow, reacting in a fixed bed reactor, and separating and purifying to obtain high-purity carbon tetrafluoride and chlorine; the alkaline earth Sr modified alumina-chromia catalyst is fluorinated in an HF atmosphere prior to use. The invention can generate carbon tetrafluoride and chlorine by one-step reaction, and has mild reaction condition and no byproduct.
Description
Technical Field
The invention relates to the technical field of carbon tetrafluoride, in particular to a method for preparing high-purity carbon tetrafluoride and chlorine.
Background
Carbon tetrafluoride (CF) 4 ) The plasma etching gas with the largest dosage in the microelectronics industry is widely used for etching thin film materials such as silicon, silicon dioxide, silicon nitride, phosphosilicate glass, tungsten and the like, and has a great deal of application in the aspects of surface cleaning of electronic devices, production of solar cells, laser technology, low-temperature refrigeration, gas insulation, leakage detection agent, control of the gesture of a space rocket, detergent, lubricant, brake fluid and the like in the production of printed circuits.
At present, various methods for preparing carbon tetrafluoride gas exist in the prior art, and mainly include a chlorofluoromethane fluorination method, a hydrofluoromethane fluorination method, a fluorocarbon synthesis method and the like. The mature process is to prepare carbon tetrafluoride by using carbon hydrofluoride and carbon chlorofluoride as carbon sources, the raw materials are expensive and easy to explode, and the synthesized product contains impurities which are not easy to remove.
Japanese patent laid-open No. Sho 61-134330 discloses the use of F in the presence of a catalyst 2 A process for preparing carbon tetrafluoride by fluoriding chloromethane. However, with the gradual disablement of CFCs and HCFCs, the source of feed materials for the chlorofluoromethane fluorination process is limited and eventually will be taken out of service.
Chinese patent No. CN101298318B discloses a method and equipment for preparing high-purity carbon tetrafluoride gasThe fluorine gas and the high-purity active carbon (more than or equal to 90 percent) are used for chemical synthesis reaction, but a plurality of byproducts (C) are generated in the process 2 F 6 、C 3 F 8 Etc.), the difficulty of separating the subsequent products is increased.
In addition, cl 2 Is a very important chemical product and basic raw material, and is widely applied to the chemical, metallurgical, papermaking, textile, medicine, petrochemical and environmental protection industries. The chlorine-related products in China have more than 200 kinds, the main varieties have more than 70 kinds, and Cl 2 Represents a state of the chemical industry development. However, chlorine utilization is low in most chlorine-containing product manufacturing processes.
Chinese patent No. CN115814815a discloses a method for preparing hydrogen chloride catalytic oxidation catalyst based on alloy carrier, which uses hydrogen chloride as raw material, ruthenium is loaded on iron-chromium-aluminum alloy carrier as catalyst, and catalytic oxidation is carried out to prepare chlorine. However, the ruthenium-based catalyst is expensive, the oxygen-enriched reaction condition or the addition of an auxiliary agent or a carrier binder definitely further increases the operation cost of the process, and the application of the HCl catalytic oxidation reaction process technology is greatly restricted.
In summary, a method for preparing carbon tetrafluoride and chlorine by using carbon tetrachloride as a raw material through a one-step reaction has not been disclosed in the prior art.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art, provides a method for preparing high-purity carbon tetrafluoride and chlorine, can generate carbon tetrafluoride and chlorine by one-step reaction, has mild reaction process conditions and has no byproducts.
The technical scheme of the invention is as follows:
the method for preparing high-purity carbon tetrafluoride and chlorine gas uses carbon tetrachloride as raw material, uses alkaline earth metal Sr modified alumina-chromium oxide as catalyst, introduces fluorine-containing gas flow, makes reaction in fixed bed reactor, and makes separation and purification (washing to remove unreacted CCl) 4 And F 2 And then rectifying and separating to obtain high-purity carbon tetrafluoride and chlorine;
the preparation method of the alkaline earth metal Sr modified alumina-chromia catalyst comprises the following steps:
s1: al is added with 2 O 3 Placing the pellets in a muffle furnace, heating to 800-1200 ℃ and roasting for 4-8 hours;
s2: preparation of CrCl 3 And strontium salts (such as strontium nitrate or chloride);
s3: regulating the pH value of the mixed solution prepared in the step S2 to 6-9, and mixing the mixed solution with the Al roasted in the step S1 2 O 3 Stirring and mixing, standing and ageing for 1-4h, filtering, drying at 120-200 ℃ for 4-8h, and roasting in a muffle furnace at 400-600 ℃ for 4-8h;
before using, the alkaline earth metal Sr modified alumina-chromia catalyst is fluorinated in HF atmosphere under the following conditions: at N 2 Drying for 6-10h at 100-200 ℃; during fluorination, the flow rate of the HF is 10-30g/h, the fluorination time is 4-8h, and the fluorination temperature is 300-350 ℃.
Preferably, the reaction temperature is 80-120 ℃, and the reaction pressure is normal pressure.
Preferably, the molar ratio of carbon tetrachloride to fluorine is 1 (1-5).
Preferably, the gas flow containing fluorine is a mixed gas of fluorine and nitrogen, wherein the volume ratio of fluorine is 50-70%.
Preferably, the gas flow containing fluorine is a mixed gas of fluorine and nitrogen, wherein the volume ratio of fluorine is 50-60%.
The reaction of carbon tetrachloride and fluorine gas is exothermic, and other gases in the fluorine-containing gas flow are used for diluting the concentration of the fluorine gas, so that the reaction is ensured to be carried out safely.
Preferably, in step S2, crCl 3 And strontium salt, wherein the molar ratio of Cr to Sr element is (2-6): 1.
Preferably, in step S2, crCl 3 And strontium salt, wherein the mole ratio of Cr to Sr element is (3-5): 1.
Preferably, in step S2, the strontium salt is nitrate or chloride.
Preferably, in step S2, the strontium salt is a chloride salt.
Preferably, in step S2, the strontium salt is SrCl 2 ·6H 2 O。
Preferably, in step S3, the molar ratio of Cr to Al element is 1 (1-7).
Preferably, in step S3, the molar ratio of Cr to Al element is 1 (3-6).
Preferably, in step S3, the molar ratio of Cr to Al element is 1 (3-5).
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts carbon tetrachloride and fluorine gas as raw materials, carbon tetrafluoride and chlorine can be generated by one-step reaction, the reaction process condition is mild, and no by-product is generated; the prepared carbon tetrafluoride and chlorine gas products have high purity, high value, simple separation process and easy operation; and washed with water, unreacted raw material CCl 4 Can be separated from water and can be recovered and reused after being dried.
2. The alkaline earth metal Sr modified alumina-chromia catalyst prepared by the invention has the advantages of simple preparation flow, low cost and good catalytic performance indexes, can greatly reduce the contact time of carbon tetrachloride and fluorine gas, and ensures the rapid and stable operation of the reaction.
Detailed Description
In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below in connection with the embodiments of the present invention.
The raw materials in the present invention are all commercially available, and the apparatus used in the present invention can be carried out using conventional apparatuses in the art or referring to the prior art in the art.
The invention detects the material composition and the content of the reaction product by helium ion gas chromatography (GC-6600): first, through CF 4 And Cl 2 CF determination by standard of (c) 4 And Cl 2 The position of the peak in the gas chromatograph; in order to ensure the safety of experimental analysis, the reaction products are collected by an air bag, washed by water, sampled and then subjected to chromatographic analysis; because after washing with water, cl 2 Will be partially dissolved in water, so that Cl is actually generated 2 Is higher than the content of chromatographic fractionAnd (5) analyzing the result.
Example 1
The preparation method of the alkaline earth metal Sr modified chromium oxide-aluminum oxide catalyst of the present embodiment comprises the following steps:
s1: will be commercially available Al 2 O 3 Weighing 100g of pellets, putting into a muffle furnace, heating to 800 ℃ and roasting for 4 hours;
s2: 10g CrCl was weighed out 3 And 5g SrCl 2 ·6H 2 O is dissolved in 50mL of deionized water, heated and stirred for dissolution, and a mixed solution is obtained;
s3: by adding KOH dropwise to the mixed solution, adjusting the pH of the mixed solution to 6, heating it to 60℃and adding 30g of calcined Al thereto 2 O 3 Stirring for 5min, standing and aging for 2h, and filtering when the solution becomes colorless; drying at 120 ℃ for 6 hours, transferring into a muffle furnace, and roasting at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst;
s4, fluorination of the catalyst: 10mL of catalyst was measured and placed in a fixed bed reactor, at N 2 After drying by purging at 200℃for 6 hours, HF was introduced and the flow rate was controlled at 20g/h and fluorinated at 300℃for 4 hours.
Heating the preheater and the fixed bed reactor to 120 ℃, preheating all raw materials by the preheater, and then entering the fixed bed reactor for reaction. Introducing carbon tetrachloride into the preheater, controlling the blanking rate to be 8g/h, and then mixing and introducing 35mL/min fluorine gas and 30mL/min N 2 Carrying out reaction under normal pressure; the reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 1.
Example 2
The preparation method of the alkaline earth metal Sr modified chromium oxide-aluminum oxide catalyst of the present embodiment comprises the following steps:
s1: will be commercially available Al 2 O 3 Weighing 100g of pellets, putting into a muffle furnace, heating to 900 ℃ and roasting for 6 hours;
s2: weigh 12g CrCl 3 And 5g SrCl 2 ·6H 2 O is dissolved in 50mL of deionized water, heated and stirred for dissolution, and a mixed solution is obtained;
s3: by direction ofDropwise adding KOH into the mixed solution, regulating the pH of the mixed solution to 7, heating the mixed solution to 60 ℃, and adding 30g of baked Al into the mixed solution 2 O 3 Stirring for 7min, standing and aging for 2h, and filtering when the solution becomes colorless; drying at 200 ℃ for 6 hours, transferring into a muffle furnace, and roasting at 500 ℃ for 5 hours in an air atmosphere to obtain a catalyst;
s4, fluorination of the catalyst: 10mL of catalyst was measured and placed in a fixed bed reactor, at N 2 After drying for 6 hours at 200℃under purging, HF was introduced and the flow rate was controlled at 10g/h and fluorinated for 6 hours at 300 ℃.
Heating the preheater and the fixed bed reactor to 80 ℃, preheating all raw materials by the preheater, and then entering the fixed bed reactor for reaction. Introducing carbon tetrachloride into the preheater, controlling the blanking rate to be 2g/h, and then mixing and introducing 15mL/min fluorine gas and 10 mL/min N 2 Carrying out reaction under normal pressure; the reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 1.
Example 3
The preparation method of the alkaline earth metal Sr modified chromium oxide-aluminum oxide catalyst of the present embodiment comprises the following steps:
s1: will be commercially available Al 2 O 3 Weighing 100g of pellets, putting into a muffle furnace, heating to 1000 ℃ and roasting for 8 hours;
s2: weigh 15g CrCl 3 And 5g SrCl 2 ·6H 2 O is dissolved in 50mL of deionized water, heated and stirred for dissolution, and a mixed solution is obtained;
s3: by adding KOH dropwise to the mixed solution, the pH of the mixed solution was adjusted to 7.5, and after heating to 60℃30g of calcined Al was added thereto 2 O 3 Stirring for 10min, standing and aging for 2h, and filtering when the solution becomes colorless; drying at 150 ℃ for 6 hours, transferring into a muffle furnace, and roasting at 500 ℃ for 5 hours in an air atmosphere to obtain a catalyst;
s4, fluorination of the catalyst: 10mL of catalyst was measured and placed in a fixed bed reactor, at N 2 After drying for 6h at 200℃under purging, HF was introduced at a flow rate of 20g/h, at 350Fluorinated for 8h at C.
Heating the preheater and the fixed bed reactor to 100 ℃, preheating all raw materials by the preheater, and then entering the fixed bed reactor for reaction. Introducing carbon tetrachloride into the preheater, controlling the blanking of the carbon tetrachloride to be 5g/h, and then mixing and introducing 35mL/min fluorine gas and 30mL/min N 2 Carrying out reaction under normal pressure; the reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 1.
Example 4
The preparation method of the alkaline earth metal Sr modified chromium oxide-aluminum oxide catalyst of the present embodiment comprises the following steps:
s1: will be commercially available Al 2 O 3 Weighing 100g of pellets, putting into a muffle furnace, heating to 800 ℃ and roasting for 8 hours;
s2: weigh 8.5g CrCl 3 And 7g SrCl 2 ·6H 2 O is dissolved in 50mL of deionized water, heated and stirred for dissolution, and a mixed solution is obtained;
s3: by adding KOH dropwise to the mixed solution, the pH of the mixed solution was adjusted to 8.5, and after heating to 60℃30g of calcined Al was added thereto 2 O 3 Stirring for 8min, standing and aging for 4h, and filtering when the solution becomes colorless; drying at 120 ℃ for 4 hours, transferring into a muffle furnace, and roasting at 500 ℃ for 5 hours in an atmosphere of air to obtain a catalyst;
s4, fluorination of the catalyst: 10mL of catalyst was measured and placed in a fixed bed reactor, at N 2 After drying by purging at 100℃for 10 hours, HF was introduced and the flow rate was controlled at 20g/h and fluorinated at 300℃for 8 hours.
Heating the preheater and the fixed bed reactor to 120 ℃, preheating all raw materials by the preheater, and then entering the fixed bed reactor for reaction. Introducing carbon tetrachloride into the preheater, controlling the blanking rate to be 8g/h, and then mixing and introducing 55mL/min fluorine gas and 45mL/min N 2 Carrying out reaction under normal pressure; the reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 1.
Example 5
The procedure of example 1 is followed, withoutThe method is characterized in that: feeding 5g/h of carbon tetrachloride, and mixing and introducing 60mL/min of fluorine gas and 30mL/min of N 2 The method comprises the steps of carrying out a first treatment on the surface of the The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 1.
Example 6
The preparation method of the alkaline earth metal Sr modified chromium oxide-aluminum oxide catalyst of the present embodiment comprises the following steps:
s1: will be commercially available Al 2 O 3 Weighing 100g of pellets, putting into a muffle furnace, heating to 1200 ℃ and roasting for 8 hours;
s2: weigh 17.5g CrCl 3 And 5g SrCl 2 ·6H 2 O is dissolved in 50mL of deionized water, heated and stirred for dissolution, and a mixed solution is obtained;
s3: by adding KOH dropwise to the mixed solution, the pH of the mixed solution was adjusted to 8.5, and after heating to 60 ℃, 12g of calcined Al was added thereto 2 O 3 Stirring for 10min, standing and aging for 2h, and filtering when the solution becomes colorless; drying at 120 ℃ for 8 hours, transferring into a muffle furnace, and roasting at 400 ℃ for 8 hours in an air atmosphere to obtain a catalyst;
s4, fluorination of the catalyst: 10mL of catalyst was measured and placed in a fixed bed reactor, at N 2 After drying for 8 hours at 200℃with purging, HF was introduced and the flow rate was controlled at 30g/h and fluorinated for 8 hours at 350 ℃.
Heating the preheater and the fixed bed reactor to 120 ℃, preheating all raw materials by the preheater, and then entering the fixed bed reactor for reaction. Introducing carbon tetrachloride into the preheater, controlling the blanking rate to be 2g/h, and then mixing and introducing 15mL/min fluorine gas and 10 mL/min N 2 Carrying out reaction under normal pressure; the reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 1.
Example 7
The preparation method of the alkaline earth metal Sr modified chromium oxide-aluminum oxide catalyst of the present embodiment comprises the following steps:
s1: will be commercially available Al 2 O 3 Weighing 100g of pellets, putting into a muffle furnace, heating to 1200 ℃ and roasting for 4 hours;
s2: 10g CrCl was weighed out 3 And 5g SrCl 2 ·6H 2 O is dissolved in 50mL of deionized water, heated and stirred for dissolution, and a mixed solution is obtained;
s3: by adding KOH dropwise to the mixed solution, adjusting the pH of the solution to 9, heating it to 80℃and adding 45g of calcined Al thereto 2 O 3 Stirring for 7min, standing and aging for 1h, and filtering when the solution becomes colorless; drying at 180 ℃ for 4 hours, transferring into a muffle furnace, and roasting at 600 ℃ for 4 hours in an air atmosphere to obtain a catalyst;
s4, fluorination of the catalyst: 10mL of catalyst was measured and placed in a fixed bed reactor, at N 2 After drying by purging at 150℃for 6 hours, HF was introduced and the flow rate was controlled at 10g/h and fluorinated at 330℃for 4 hours.
Heating the preheater and the fixed bed reactor to 90 ℃, preheating all raw materials by the preheater, and then entering the fixed bed reactor for reaction. Introducing carbon tetrachloride into the preheater, controlling the blanking rate to be 2g/h, and then mixing and introducing 15mL/min fluorine gas and 10 mL/min N 2 Carrying out reaction under normal pressure; the reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 1.
Example 8
The procedure is as in example 1, except that: in preparing the catalyst, sr (NO) 3 ) 2 Equivalent replacement of SrCl 2 ·6H 2 O. The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 1.
As can be seen from a comparison of example 1 and example 8 in Table 1, the different Sr source pairs CCl 4 Has an influence on the conversion of CCl when the chloride salt of Sr is used 4 The conversion was about 10% higher than the nitrate. The reason may be that the precursors of the Sr source and the Cr source are both chloride salts, the anions are the same and have the same acting force on the metal cations, and different anions in the precursor may have different acting forces on the metal, thereby leading to different catalyst performances.
Example 9
The procedure is as in example 1, except that:in the preparation of the catalyst, al after calcination 2 O 3 The amount of (2) added was 20g. The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 1.
TABLE 1 results of gas chromatography analyses of examples 1-9
As can be seen from Table 1, in the above embodiment, CCl 4 The conversion of (2) varies, but divided by CCl 4 And Cl 2 No other by-products were found to be produced, CF 4 The selectivities of (a) and (b) are all 100%; because of Cl 2 After washing with water, part of the solution is dissolved in water, so Cl 2 And cannot be accurately quantified.
Comparative example 1
The procedure is as in example 1, except that: the fixed bed reactor is not filled with an alkaline earth metal Sr modified chromium oxide-aluminum oxide catalyst. The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 2.
As can be seen from Table 2, CCl of comparative example 1 is compared with example 1 4 The conversion rate is greatly reduced, the reason is that the reaction condition is mild, the catalyst is not added enough to overcome the reaction activation energy, namely the catalyst has insufficient activity and has a certain influence on the selectivity, thereby leading to CCl 4 The conversion efficiency is reduced and intermediate byproducts are formed.
Comparative example 2
The procedure is as in example 2, except that: srCl is not added 2 ·6H 2 O. The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 2.
As can be seen from Table 2, CCl is compared with example 2 4 The conversion rate and the selectivity of the main product are obviously reduced, CCl 4 The conversion of (2) was reduced by about 15%. This is probably because there is an interaction between Sr and Cr, al elements, and no Sr element is added, the interaction is weakened, i.e., the electricity between ionsThe sub-effect becomes weaker, leading to CCl 4 The conversion and the selectivity of the main product are reduced.
Comparative example 3
The procedure is as in example 1, except that: the catalyst is not subjected to the fluorination treatment of step S4. The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 2.
As can be seen from Table 2, the CCl of comparative example 3 is compared with example 1 4 Conversion ratio of CCl of example 1 4 The conversion is reduced by 32.16% because the catalyst is not able to form significant amounts of active components when the catalyst is not fluorinated, resulting in insufficient active sites to form carbon tetrafluoride during the carbon tetrachloride reaction, and in reduced conversion, resulting in the formation of intermediate byproducts.
Comparative example 4
The procedure is as in example 1, except that: step S4, fluorination is carried out on the catalyst: 10mL of catalyst was measured and placed in a fixed bed reactor, at N 2 After drying for 6 hours at 200℃under purging, HF was introduced and the flow was controlled at 40g/h and the fluorination temperature was 400℃for 10 hours. After the fluorination is finished, the catalyst is green.
As can be seen from table 2, the catalyst activity of comparative example 4 was lowered compared with example 1, probably because the catalyst was excessively fluorinated, so that the catalyst was crystallized, i.e., the catalyst structure was changed, and the catalyst was represented as green, thereby causing the catalyst activity to be lowered and by-products to be generated.
Comparative example 5
The preparation method of the chromium oxide catalyst of comparative example 5 comprises the following steps:
s1: 10g CrCl was weighed out 3 Dissolving in 50mL of deionized water, heating, stirring and dissolving to obtain a solution;
s2: dropwise adding KOH into the solution, regulating the pH value to 6, standing and aging for 2 hours, and filtering; drying at 120deg.C for 6h, transferring into a muffle furnace, and roasting at 400deg.C for 4h in air atmosphere;
s3, fluorination of the catalyst: 10mL of catalyst was measured and placed in a fixed bed reactor, at N 2 After drying for 6 hours at 200℃under purging, HF was introduced and the flow was controlled at 20g/h and the fluorination temperature was 300℃for 4 hours.
Heating the preheater and the fixed bed reactor to 120 ℃, preheating all raw materials by the preheater, and then entering the fixed bed reactor for reaction. Introducing carbon tetrachloride into the preheater, controlling the blanking rate to be 8g/h, and then mixing and introducing 35mL/min fluorine gas and 30mL/min N 2 Carrying out reaction under normal pressure; the reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 2.
Comparative example 6
The alumina catalyst preparation method of comparative example 6 includes the steps of:
s1: will be commercially available Al 2 O 3 Weighing 100g of pellets, putting into a muffle furnace, heating to 800 ℃ and roasting for 4 hours;
s2, fluorination of the catalyst: 10mL of catalyst was measured and placed in a fixed bed reactor, at N 2 After drying for 6 hours at 200℃under purging, HF was introduced and the flow was controlled at 20g/h and the fluorination temperature was 300℃for 4 hours.
Heating the preheater and the fixed bed reactor to 120 ℃, preheating all raw materials by the preheater, and then entering the fixed bed reactor for reaction. Introducing carbon tetrachloride into the preheater, controlling the blanking rate to be 8g/h, and then mixing and introducing 35mL/min fluorine gas and 30mL/min N 2 Carrying out reaction under normal pressure; the reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 2.
As can be seen from Table 2, CCl of comparative examples 5 to 6 compared with examples 4 The conversion rate is obviously reduced, and byproducts are generated; the conversion and the selectivity of the main product are improved compared with those of comparative example 1. The reason may be that the chromium oxide catalyst is a single component catalyst, and there is no interaction between elements, so that the catalytic effect is insignificant.
Comparative example 7
The procedure is as in example 1, except that: in the preparation of the catalyst, 15g SrCl was used 2 ·6H 2 O replaces 5g SrCl 2 ·6H 2 O. The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 2.
As can be seen from Table 2, the CCl of comparative example 7 is compared with example 1 4 The conversion rate is obviously reduced, and byproducts are generated. The reason may be that the addition amount of Sr is excessive, covering part of the active sites on the catalyst, so that the catalyst activity is reduced as a whole.
Comparative example 8
The procedure is as in example 1, except that: in the preparation of the catalyst, al after calcination 2 O 3 The amount of (2) added was 50g. The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 2.
As can be seen from Table 2, the CCl of comparative example 8 is compared with example 1 4 The conversion was reduced by 23.3% and byproducts were produced. The reason may be Al 2 O 3 Excessive addition amount causes too dispersed distribution of Cr and Sr to affect Cr 3+ 、Sr 2+ And Al 3+ The interaction between the two results in overall reduced catalyst activity.
Comparative example 9
The procedure is as in example 1, except that: in step S3, the pH of the mixed solution is adjusted to 10. The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 2.
As can be seen from Table 2, the catalyst activity of comparative example 9 is significantly reduced as compared with example 1, because the reduction of the catalyst surface acidity leads to the reduction of the catalyst activity, leading to CCl 4 The conversion is reduced and by-products are produced.
Comparative example 10
The procedure is as in example 1, except that: in the step S4, the catalyst is fluorinated at 260 ℃. The reaction product was washed with water and analyzed for its material composition and content by gas chromatography, and the analysis results are shown in Table 2.
As can be seen from Table 2, the conversion of carbon tetrachloride in comparative example 10 was greatly reduced and intermediate by-products were produced as compared with example 1. The reason may be that the fluorination temperature of the catalyst is too low to form a large amount of effective active components, resulting in insufficient active sites to form carbon tetrafluoride during the carbon tetrachloride reaction, and thus the conversion is reduced and also results in the formation of intermediate byproducts.
TABLE 2 results of gas chromatography analyses of comparative examples 1-10
In conclusion, carbon tetrachloride and fluorine gas are used as raw materials, carbon tetrafluoride and chlorine can be generated by one-step reaction, the reaction process condition is mild, and no byproducts are generated; the prepared carbon tetrafluoride and chlorine gas products have high purity and high value.
Claims (7)
1. The method for preparing the high-purity carbon tetrafluoride and chlorine is characterized in that carbon tetrachloride is used as a raw material, alkaline earth metal Sr modified alumina-chromium oxide is used as a catalyst, fluorine-containing gas flow is introduced, the reaction is carried out in a fixed bed reactor, and the high-purity carbon tetrafluoride and the chlorine are obtained after separation and purification;
the preparation method of the alkaline earth metal Sr modified alumina-chromia catalyst comprises the following steps:
s1: al is added with 2 O 3 Placing the pellets in a muffle furnace, heating to 800-1200 ℃ and roasting for 4-8 hours;
s2: preparation of CrCl 3 And strontium salt mixed solution;
s3: regulating the pH value of the mixed solution prepared in the step S2 to 6-9, and mixing the mixed solution with the Al roasted in the step S1 2 O 3 Stirring and mixing, standing and ageing for 1-4h, filtering, drying at 120-200 ℃ for 4-8h, and roasting in a muffle furnace at 400-600 ℃ for 4-8h;
before using, the alkaline earth metal Sr modified alumina-chromia catalyst is fluorinated in HF atmosphere under the following conditions: at N 2 Drying for 6-10h at 100-200 ℃; during fluorination, the flow rate of the HF is 10-30g/h, the fluorination time is 4-8h, and the fluorination temperature is 300-350 ℃.
2. The method for preparing high purity carbon tetrafluoride and chlorine according to claim 1, wherein the reaction temperature is 80 to 120 ℃ and the reaction pressure is normal pressure.
3. The method for preparing high purity carbon tetrafluoride and chlorine according to claim 1, wherein the molar ratio of carbon tetrachloride to fluorine is 1 (1-5).
4. The method for producing high-purity carbon tetrafluoride and chlorine according to claim 1, wherein the fluorine-containing gas stream is a mixed gas of fluorine gas and nitrogen gas, and wherein the volume ratio of fluorine gas is 50 to 70%.
5. The method for producing high purity carbon tetrafluoride and chlorine gas according to claim 1, wherein CrCl is used in step S2 3 And strontium salt, wherein the molar ratio of Cr to Sr element is (2-6): 1.
6. The method for preparing high purity carbon tetrafluoride and chlorine gas according to claim 1, wherein in step S2, the strontium salt is nitrate or chloride.
7. The method for producing high-purity carbon tetrafluoride and chlorine gas according to claim 1, wherein in step S3, the molar ratio of Cr to Al element is 1 (1-7).
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| US3386989A (en) * | 1966-08-23 | 1968-06-04 | Du Pont | Process for continuous production of carbon tetrafluoride |
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| CN101269323A (en) * | 2008-04-23 | 2008-09-24 | 浙江师范大学 | Catalyst for producing tetrafluoromethane with gas-phase fluoridation and production method |
| CN101723797A (en) * | 2008-10-16 | 2010-06-09 | 浙江师范大学 | Method for producing tetrafluoromethane by gas phase catalysis |
| CN108863710A (en) * | 2018-06-20 | 2018-11-23 | 临海市利民化工有限公司 | A kind of preparation method of tetrafluoromethane |
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| US3386989A (en) * | 1966-08-23 | 1968-06-04 | Du Pont | Process for continuous production of carbon tetrafluoride |
| JPH0920695A (en) * | 1995-07-05 | 1997-01-21 | Showa Denko Kk | Production of tetrafluoromethane |
| CN101269323A (en) * | 2008-04-23 | 2008-09-24 | 浙江师范大学 | Catalyst for producing tetrafluoromethane with gas-phase fluoridation and production method |
| CN101723797A (en) * | 2008-10-16 | 2010-06-09 | 浙江师范大学 | Method for producing tetrafluoromethane by gas phase catalysis |
| CN108863710A (en) * | 2018-06-20 | 2018-11-23 | 临海市利民化工有限公司 | A kind of preparation method of tetrafluoromethane |
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