CN110563545B - Continuous industrial preparation method of octafluorocyclopentene - Google Patents
Continuous industrial preparation method of octafluorocyclopentene Download PDFInfo
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- YBMDPYAEZDJWNY-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluorocyclopentene Chemical compound FC1=C(F)C(F)(F)C(F)(F)C1(F)F YBMDPYAEZDJWNY-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 17
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000013067 intermediate product Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 38
- 239000012025 fluorinating agent Substances 0.000 claims description 30
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 claims description 28
- DMZRCHJVWAKCAX-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octachlorocyclopentene Chemical compound ClC1=C(Cl)C(Cl)(Cl)C(Cl)(Cl)C1(Cl)Cl DMZRCHJVWAKCAX-UHFFFAOYSA-N 0.000 claims description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000004005 microsphere Substances 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000010445 mica Substances 0.000 claims description 9
- 229910052618 mica group Inorganic materials 0.000 claims description 9
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- ZGDNCERTFGMFLX-UHFFFAOYSA-N gadolinium silver Chemical compound [Ag].[Gd] ZGDNCERTFGMFLX-UHFFFAOYSA-N 0.000 claims description 7
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 238000002309 gasification Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229940116411 terpineol Drugs 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012071 phase Substances 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000010815 organic waste Substances 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 9
- 238000001354 calcination Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- XUMFLKOMBYRBCK-UHFFFAOYSA-N 1-chloro-2,3,3,4,4,5,5-heptafluorocyclopentene Chemical compound FC1=C(Cl)C(F)(F)C(F)(F)C1(F)F XUMFLKOMBYRBCK-UHFFFAOYSA-N 0.000 description 2
- -1 Organofluorine compounds Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZFMWDTNZPKDVBU-UHFFFAOYSA-N 1,2,3,4-tetrachlorocyclopentane Chemical compound ClC1CC(Cl)C(Cl)C1Cl ZFMWDTNZPKDVBU-UHFFFAOYSA-N 0.000 description 1
- ABPBVCKGWWGZDP-UHFFFAOYSA-N 1,2-dichloro-3,3,4,4,5,5-hexafluorocyclopentene Chemical compound FC1(F)C(Cl)=C(Cl)C(F)(F)C1(F)F ABPBVCKGWWGZDP-UHFFFAOYSA-N 0.000 description 1
- QPIRTTQWLDPXBN-UHFFFAOYSA-N 1,2-dichlorocyclopentane Chemical compound ClC1CCCC1Cl QPIRTTQWLDPXBN-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- B01J35/51—
-
- 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
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- 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
Abstract
The invention relates to the field of fine chemical engineering, in particular to a continuous industrial preparation method of octafluorocyclopentene; comprises the steps of gas phase chlorination reaction, intermediate product purification, gas phase fluorination reaction and the like; compared with the existing liquid phase fluorination method technology for preparing octafluorocyclopentene, the method for preparing octafluorocyclopentene by using the gas phase method to obtain the final product of octafluorocyclopentene from the easily obtained raw material cyclopentene has the advantages of cheap reaction raw materials, simple reaction, inapplicability to solvents, no generation of organic waste liquid, short reaction time, higher yield of the produced product, continuous production and great prospect of industrial production.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a continuous industrial preparation method of octafluorocyclopentene.
Background
Organofluorine compounds are a class of elemental organic compounds in which the hydrogen attached to a carbon atom in the molecule of the organic compound is replaced by fluorine. Since fluorine is the element with the largest electronegativity, the polyfluoro organic compound has the characteristics of chemical stability, surface activity, excellent temperature resistance and the like, and the requirements of various fluorine-containing raw materials are more and more extensive.
CN107188778A discloses a preparation method of octafluorocyclopentene, which comprises the following steps: a. in the presence of a fluorination catalyst, carrying out gas-phase catalytic fluorination reaction on 1, 4-dichlorohexachlorocyclopentene or/and 1, 3-dichlorohexachlorocyclopentene or/and 1, 2-dichlorohexafluorocyclopentene and anhydrous hydrogen fluoride to obtain an intermediate 1-chloroheptafluorocyclopentene, and b, in the presence of a fluorination catalyst, carrying out gas-phase catalytic fluorination reaction on 1-chloroheptafluorocyclopentene and anhydrous hydrogen fluoride to obtain octafluorocyclopentene. The invention can realize zero-pollution production of octafluorocyclopentene, and the first step reaction and the second step reaction can completely react materials through a circulating system, thereby realizing full utilization of the materials.
CN108276243A provides an industrial production method of octafluorocyclopentene, which is characterized in that:
first step, chlorination reaction:
introducing chlorine into the cyclopentene, adding to obtain 1, 2-dichlorocyclopentane, continuously introducing chlorine, heating to 70 ℃ for reaction to obtain 1,2,3, 4-tetrachlorocyclopentane, and continuously heating to 180 ℃ and 210 ℃ for reaction to obtain octachlorocyclopentene crude product.
And step two, substitution fluorination:
after anhydrous potassium fluoride and sulfolane are mixed, the temperature is controlled at 140-.
The yield of the reaction product is low.
CN110002948A relates to a preparation method of halogenated cycloolefins, belonging to the field of chemical synthesis. The preparation method of the invention takes halogenated cycloalkane as raw material in amide or alkylamine solvent to carry out dehalogenation reaction, thus obtaining the target product halogenated cycloalkene. The method does not need to use dangerous reducing agents such as metal or hydrogen, has safe and reliable process, does not generate waste solids such as metal halide and the like, and can effectively separate the waste solids industrially by a common distillation means.
The octafluorocyclopentene is mainly used for etching and cleaning semiconductors and can participate in the preparation of organic photochromic materials, and the methods for preparing the octafluorocyclopentene in the prior art are mostly liquid phase fluorination methods, so that the preparation reaction steps are complex, the amount of generated organic waste liquid is large, the reaction time is long, the yield of the produced product is low, continuous production cannot be realized, and the possibility of industrial production is limited.
Most of the gas phase fluorination catalysts used in practice are chromium-containing catalysts, and it has been proved that chromium compounds are toxic and cause damage to the digestive tract and kidney of humans, and high-valent chromium has a strong carcinogenic effect and is harmful to humans and the environment in production and use. The chromium-free catalyst limited in the technology has the problems of poor catalytic activity and easy loss, and the use effect is influenced.
Disclosure of Invention
In order to solve the problems, the invention provides a continuous industrial preparation method of octafluorocyclopentene.
A continuous industrial preparation method of octafluorocyclopentene comprises the following specific scheme:
step one, chlorination reaction, wherein the chlorination reaction is a process of reacting cyclopentene with chlorine to generate octachlorocyclopentene; the chlorination reaction is carried out in a chlorination tower; the chlorination tower is divided into four sections from bottom to top, wherein the temperature of the first section is 80-100 ℃, the temperature of the second section is 140-; the mol ratio of the chlorine to the cyclopentene is 10-15: 1;
step two, purifying an intermediate product, namely distilling and purifying the mixed gas passing through a chlorination tower under reduced pressure to obtain octachlorocyclopentene, washing the mixed gas extracted under reduced pressure with saturated salt solution, drying and then introducing the mixed gas into the chlorination tower again for reaction;
performing fluorination reaction, namely performing gas-phase fluorine-chlorine exchange reaction on the gasified octafluorocyclopentene and anhydrous hydrogen fluoride serving as raw materials in a fluidized bed reactor under the action of a bismuth-molybdenum co-doped fluorinating agent to generate octafluorocyclopentene; the gasification temperature of the octachlorocyclopentene is 300-350 ℃; the reaction temperature in the fluidized bed reactor is 350-450 ℃, and the reaction pressure is 0.05-0.5 MPa; rectifying the product after reaction to obtain octafluorocyclopentene.
In the chlorination reaction, the residence time of the mixed gas in the first area of the chlorination tower is 3-8min, the residence time in the second area is 5-10min, the residence time in the third area is 8-12min, and the residence time in the fourth area is 8-15 min.
The contact time of the fluorination reaction in the reaction bed is 10-30 s.
The molar ratio of anhydrous hydrogen fluoride to octachlorocyclopentene in the fluorination reaction is 8-12: 1.
The bismuth-molybdenum co-doped fluorinating agent is prepared according to the following scheme:
according to the mass portion, 8-13 portions of ammonium hexafluoroaluminate micro powder, 0.1-2 portions of ammonium tetrathiomolybdate, 0.5-2 portions of solid binder nano zirconium dioxide, 0.05-0.8 portion of perfluoroalkyl silyl mica, 0.8-2.7 portions of pore-forming agent ethyl cellulose, 2-5 portions of ferric trichloride and 0.01-0.3 portion of bismuth nitrate are added into a ball milling tank, after being uniformly mixed, 35-55 portions of terpineol and 80-120 portions of ethanol are added, 0.01-0.3 portion of gadolinium silver tungstate is then ball milled for 24-36h, after the ball milling is completed, the ethanol is evaporated, the obtained slurry is prepared into microspheres with the particle size of 0.05-0.5mm on a granulator, and is dried for 20-30min at the temperature of 70-90 ℃ to obtain dried microsphere particles, then the dried microsphere particles are calcined for 1-5h at the temperature of 400 ℃, mixed gas of nitrogen and hydrogen fluoride is introduced to fluorinate at the temperature of 300-350 ℃, thus obtaining the bismuth-molybdenum codoped fluorinating agent.
The volume ratio of the mixed gas of the nitrogen and the hydrogen fluoride is 1: 0.5-3:
the invention has the technical effects that:
compared with the existing liquid phase fluorination method technology for preparing octafluorocyclopentene, the method for preparing octafluorocyclopentene by using the gas phase method to obtain the final product of octafluorocyclopentene from the easily obtained raw material cyclopentene has the advantages of cheap reaction raw materials, simple reaction, inapplicability to solvents, no generation of organic waste liquid, short reaction time, higher yield of the produced product, continuous production and great prospect of industrial production.
The bismuth-molybdenum co-doped fluorinating agent disclosed by the invention does not contain a chromium element, and has the combined action of perfluoroalkyl silyl mica, ammonium tetrathiomolybdate, bismuth nitrate and gadolinium silver tungstate, so that the fluorinating agent is endowed with a higher catalytic effect, and the highest yield of octafluorocyclopentene can reach 93.8%; perfluoroalkyl radicalThe laminated structure of the silyl mica can obtain fluoridizing agent with higher specific surface area up to 657m after metal intercalation2/g。
Drawings
FIG. 1 is a Fourier infrared spectrum of octafluorocyclopentene made in example 3.
Detailed Description
The invention is further illustrated by the following specific examples:
the specific surface area of the bismuth-molybdenum co-doped fluorinating agent produced by different schemes is tested by adopting a method for measuring the specific surface area of a GB/T2922-1982 chromatographic carrier, and the content of the final product is analyzed by adopting a gas chromatography.
Example 1
A continuous industrial preparation method of octafluorocyclopentene comprises the following specific scheme:
step one, chlorination reaction, wherein the chlorination reaction is a process of reacting cyclopentene with chlorine to generate octachlorocyclopentene; the chlorination reaction is carried out in a chlorination tower; the chlorination tower is divided into four intervals from bottom to top, wherein the temperature of the first interval is 80 ℃, the temperature of the second interval is 140 ℃, the temperature of the third interval is 180 ℃, and the temperature of the fourth interval is 210 ℃; the mol ratio of the chlorine to the cyclopentene is 10: 1;
step two, purifying an intermediate product, namely distilling and purifying the mixed gas passing through a chlorination tower under reduced pressure to obtain octachlorocyclopentene, washing the mixed gas extracted under reduced pressure with saturated salt solution, drying and then introducing the mixed gas into the chlorination tower again for reaction;
performing fluorination reaction, namely performing gas-phase fluorine-chlorine exchange reaction on the gasified octafluorocyclopentene and anhydrous hydrogen fluoride serving as raw materials in a fluidized bed reactor under the action of a bismuth-molybdenum co-doped fluorinating agent to generate octafluorocyclopentene; the gasification temperature of the octachlorocyclopentene is 300 ℃; the reaction temperature in the fluidized bed reactor is 350 ℃, and the reaction pressure is 0.05 MPa; rectifying the product after reaction to obtain octafluorocyclopentene.
In the chlorination reaction, the residence time of the mixed gas in the first area of the chlorination tower is 3 min, the residence time in the second area is 5min, the residence time in the third area is 8min, and the residence time in the fourth area is 8 min.
The contact time of the fluorination reaction in the reaction bed is 10 s.
The molar ratio of anhydrous hydrogen fluoride to octachlorocyclopentene in the fluorination reaction is 8: 1.
The bismuth-molybdenum co-doped fluorinating agent is prepared according to the following scheme:
according to the mass parts, 11 parts of ammonium hexafluoroaluminate micro powder, 1 part of ammonium tetrathiomolybdate, 0.7 part of solid binder nano zirconium dioxide, 0.09 part of perfluoroalkyl silyl mica, 1.2 parts of pore-forming agent ethyl cellulose, 3 parts of ferric trichloride and 0.08 part of bismuth nitrate are added into a ball milling tank, 41 parts of terpineol and 86 parts of ethanol are added after uniform mixing, 0.03 part of gadolinium tungstate silver is then ball milled for 29 hours, the ethanol is evaporated after ball milling is completed, the obtained slurry is prepared into microspheres with the thickness of 0.2mm on a granulator, the microspheres are dried for 25 minutes at 78 ℃ to obtain dried microsphere particles, then the microspheres are calcined for 3 hours at 470 ℃, and the mixed gas of nitrogen and hydrogen fluoride is introduced to fluorinate at 320 ℃ after calcination is completed, so that the bismuth-molybdenum co-doped fluorinating agent can be obtained.
The volume ratio of the mixed gas of the nitrogen and the hydrogen fluoride is 1:
the specific surface area of the bismuth-molybdenum co-doped fluorinating agent prepared by the experiment is 612m2(ii)/g; the purity of the octafluorocyclopentene product is 99.37 percent, and the yield is 91.3 percent.
Example 2
A continuous industrial preparation method of octafluorocyclopentene comprises the following specific scheme:
step one, chlorination reaction, wherein the chlorination reaction is a process of reacting cyclopentene with chlorine to generate octachlorocyclopentene; the chlorination reaction is carried out in a chlorination tower; the chlorination tower is divided into four intervals from bottom to top, wherein the temperature of the first interval is 90 ℃, the temperature of the second interval is 150 ℃, the temperature of the third interval is 190 ℃, and the temperature of the fourth interval is 220 ℃; the mol ratio of the chlorine to the cyclopentene is 13: 1;
step two, purifying an intermediate product, namely distilling and purifying the mixed gas passing through a chlorination tower under reduced pressure to obtain octachlorocyclopentene, washing the mixed gas extracted under reduced pressure with saturated salt solution, drying and then introducing the mixed gas into the chlorination tower again for reaction;
performing fluorination reaction, namely performing gas-phase fluorine-chlorine exchange reaction on the gasified octafluorocyclopentene and anhydrous hydrogen fluoride serving as raw materials in a fluidized bed reactor under the action of a bismuth-molybdenum co-doped fluorinating agent to generate octafluorocyclopentene; the gasification temperature of the octachlorocyclopentene is 330 ℃; the reaction temperature in the fluidized bed reactor is 380 ℃, and the reaction pressure is 0.25 MPa; rectifying the product after reaction to obtain octafluorocyclopentene.
In the chlorination reaction, the residence time of the mixed gas in the first area of the chlorination tower is 5min, the residence time in the second area is 8min, the residence time in the third area is 10min, and the residence time in the fourth area is 12 min.
The contact time of the fluorination reaction in the reaction bed is 20 s.
The molar ratio of anhydrous hydrogen fluoride to octachlorocyclopentene in the fluorination reaction is 10: 1.
The bismuth-molybdenum co-doped fluorinating agent is prepared according to the following scheme:
adding 8 parts of ammonium hexafluoroaluminate micro powder, 0.1 part of ammonium tetrathiomolybdate, 0.5 part of solid binder nano zirconium dioxide, 0.05 part of perfluoroalkyl silyl mica, 0.8 part of pore-forming agent ethyl cellulose, 2 parts of ferric trichloride and 0.01 part of bismuth nitrate into a ball-milling tank, uniformly mixing, adding 35 parts of terpineol and 80 parts of ethanol, 0.01 part of silver gadolinium tungstate, carrying out ball milling for 24 hours, drying the ethanol by distillation after the ball milling is finished, preparing the obtained slurry into microspheres with the thickness of 0.05mm on a granulator, drying the microspheres for 20 minutes at 70 ℃ to obtain dried microsphere particles, calcining the microspheres for 1 hour at 400 ℃, introducing mixed gas of nitrogen and hydrogen fluoride after the calcination, and fluorinating the microspheres at 300 ℃ to obtain the bismuth-molybdenum co-doped fluorinating agent.
The volume ratio of the mixed gas of the nitrogen and the hydrogen fluoride is 1: 0.5:
the specific surface area of the bismuth-molybdenum co-doped fluorinating agent prepared by the experiment is 632m2(ii)/g; purity of octafluorocyclopentene productThe degree was 99.56%, and the yield was 91.7%.
Example 3
A continuous industrial preparation method of octafluorocyclopentene comprises the following specific scheme:
step one, chlorination reaction, wherein the chlorination reaction is a process of reacting cyclopentene with chlorine to generate octachlorocyclopentene; the chlorination reaction is carried out in a chlorination tower; the chlorination tower is divided into four intervals from bottom to top, wherein the temperature of the first interval is 100 ℃, the temperature of the second interval is 160 ℃, the temperature of the third interval is 200 ℃, and the temperature of the fourth interval is 230 ℃; the mol ratio of the chlorine to the cyclopentene is 15: 1;
step two, purifying an intermediate product, namely distilling and purifying the mixed gas passing through a chlorination tower under reduced pressure to obtain octachlorocyclopentene, washing the mixed gas extracted under reduced pressure with saturated salt solution, drying and then introducing the mixed gas into the chlorination tower again for reaction;
performing fluorination reaction, namely performing gas-phase fluorine-chlorine exchange reaction on the gasified octafluorocyclopentene and anhydrous hydrogen fluoride serving as raw materials in a fluidized bed reactor under the action of a bismuth-molybdenum co-doped fluorinating agent to generate octafluorocyclopentene; the gasification temperature of the octachlorocyclopentene is 350 ℃; the reaction temperature in the fluidized bed reactor is 450 ℃, and the reaction pressure is 0.5 MPa; rectifying the product after reaction to obtain octafluorocyclopentene.
In the chlorination reaction, the residence time of the mixed gas in the first area of the chlorination tower is 8min, the residence time in the second area is 10min, the residence time in the third area is 12min, and the residence time in the fourth area is 15 min.
The contact time of the fluorination reaction in the reaction bed is 30 s.
The molar ratio of anhydrous hydrogen fluoride to octachlorocyclopentene in the fluorination reaction is 12: 1.
The bismuth-molybdenum co-doped fluorinating agent is prepared according to the following scheme:
according to the mass parts, 13 parts of ammonium hexafluoroaluminate micro powder, 2 parts of ammonium tetrathiomolybdate, 2 parts of solid binder nano zirconium dioxide, 0.05 part of perfluoroalkyl silyl mica, 2.7 parts of pore-forming agent ethyl cellulose, 5 parts of ferric trichloride and 0.3 part of bismuth nitrate are added into a ball-milling tank, 55 parts of terpineol, 120 parts of ethanol and 0.3 part of gadolinium silver tungstate are added after uniform mixing, ball milling is carried out for 36 hours, the ethanol is evaporated after the ball milling is finished, the obtained slurry is prepared into microspheres with the thickness of 0.5mm on a granulator, the microspheres are dried for 30 minutes at the temperature of 90 ℃ to obtain dried microsphere particles, then the microspheres are calcined for 1 to 5 hours at the temperature of 00 ℃, and the mixed gas of nitrogen and hydrogen fluoride is introduced to carry out fluorination at the temperature of 350 ℃ after the calcination is finished, so that the bismuth molybdenum fluoride co-doping agent is obtained.
The volume ratio of the mixed gas of the nitrogen and the hydrogen fluoride is 1: 3:
the specific surface area of the bismuth-molybdenum co-doped fluorinating agent prepared by the experiment is 657m2(ii)/g; the purity of the octafluorocyclopentene product is 99.96 percent, and the yield is 93.8 percent.
Example 4
A continuous industrial preparation method of octafluorocyclopentene comprises the following specific scheme:
step one, chlorination reaction, wherein the chlorination reaction is a process of reacting cyclopentene with chlorine to generate octachlorocyclopentene; the chlorination reaction is carried out in a chlorination tower; the chlorination tower is divided into four intervals from bottom to top, wherein the temperature of the first interval is 90 ℃, the temperature of the second interval is 150 ℃, the temperature of the third interval is 190 ℃, and the temperature of the fourth interval is 220 ℃; the mol ratio of the chlorine to the cyclopentene is 13: 1;
step two, purifying an intermediate product, namely distilling and purifying the mixed gas passing through a chlorination tower under reduced pressure to obtain octachlorocyclopentene, washing the mixed gas extracted under reduced pressure with saturated salt solution, drying and then introducing the mixed gas into the chlorination tower again for reaction;
performing fluorination reaction, namely performing gas-phase fluorine-chlorine exchange reaction on the gasified octafluorocyclopentene and anhydrous hydrogen fluoride serving as raw materials in a fluidized bed reactor under the action of a bismuth-molybdenum co-doped fluorinating agent to generate octafluorocyclopentene; the gasification temperature of the octachlorocyclopentene is 330 ℃; the reaction temperature in the fluidized bed reactor is 380 ℃, and the reaction pressure is 0.25 MPa; rectifying the product after reaction to obtain octafluorocyclopentene.
In the chlorination reaction, the residence time of the mixed gas in the first area of the chlorination tower is 4min, the residence time in the second area is 6in, the residence time in the third area is 9min, and the residence time in the fourth area is 14 min.
The contact time of the fluorination reaction in the reaction bed is 25 s.
The molar ratio of anhydrous hydrogen fluoride to octachlorocyclopentene in the fluorination reaction is 10: 1.
The bismuth-molybdenum co-doped fluorinating agent is prepared according to the following scheme:
adding 8 parts of ammonium hexafluoroaluminate micro powder, 2 parts of ammonium tetrathiomolybdate, 0.5 part of solid binder nano zirconium dioxide, 0.8 part of perfluoroalkyl silyl mica, 2.7 parts of pore-forming agent ethyl cellulose, 2 parts of ferric trichloride and 0.3 part of bismuth nitrate into a ball-milling tank, uniformly mixing, adding 35 parts of terpineol, 120 parts of ethanol and 0.01 part of gadolinium silver tungstate, then carrying out ball milling for 36 hours, drying the ethanol by distillation after the ball milling is finished, preparing the obtained slurry into microspheres with the thickness of 0.05mm on a granulator, drying the microspheres for 20 minutes at 90 ℃ to obtain dried microsphere particles, then calcining the microspheres for 1 hour at 500 ℃, introducing mixed gas of nitrogen and hydrogen fluoride to fluorinate at 300 ℃ after the calcination is finished, and obtaining the bismuth molybdenum fluorinating agent.
The volume ratio of the mixed gas of the nitrogen and the hydrogen fluoride is 1: 2:
the specific surface area of the bismuth-molybdenum co-doped fluorinating agent prepared by the experiment is 643m2(ii)/g; the purity of the octafluorocyclopentene product is 99.47 percent, and the yield is 92.1 percent.
Comparative example 1
The procedure is as in example 1 except that the nano-zirconia is not added.
The bismuth-molybdenum co-doped fluorinating agent prepared by the experiment is not formed and cannot perform catalytic reaction.
Comparative example 2
The procedure is as in example 1 except that ammonium tetrathiomolybdate is not added.
The specific surface area of the bismuth-molybdenum co-doped fluorinating agent prepared by the experiment is 407m2(ii)/g; the purity of the octafluorocyclopentene product is 96.34 percent, and the yield is 85.1 percent.
Comparative example 3
The procedure of example 1 was repeated except that bismuth nitrate was not added.
The specific surface area of the bismuth-molybdenum co-doped fluorinating agent prepared by the experiment is 579m2(ii)/g; the purity of the octafluorocyclopentene product is 97.48%, and the yield is 75.21%.
Comparative example 4
The blank is prepared without adding bismuth and molybdenum codoping fluorinating agent, and the method is otherwise the same as that of example 1.
Can not perform catalytic reaction
Comparative example 5
The procedure of example 1 was repeated except that silver gadolinium tungstate was not added.
The specific surface area of the bismuth-molybdenum co-doped fluorinating agent prepared by the experiment is 528m2(ii)/g; the purity of the octafluorocyclopentene product is 98.27%, and the yield is 81.6%.
Comparative example 6
The procedure of example 1 was repeated except that no perfluoroalkylsilyl mica was added.
The specific surface area of the bismuth-molybdenum co-doped fluorinating agent prepared by the experiment is 583m2(ii)/g; the purity of the octafluorocyclopentene product is 97.6 percent, and the yield is 85.3 percent.
Claims (5)
1. A continuous industrial preparation method of octafluorocyclopentene comprises the following specific scheme:
step one, chlorination reaction, wherein the chlorination reaction is a process of reacting cyclopentene with chlorine to generate octachlorocyclopentene; the chlorination reaction is carried out in a chlorination tower; the chlorination tower is divided into four sections from bottom to top, wherein the temperature of the first section is 80-100 ℃, the temperature of the second section is 140-; the mol ratio of the chlorine to the cyclopentene is 10-15: 1;
step two, purifying an intermediate product, namely distilling and purifying the mixed gas passing through a chlorination tower under reduced pressure to obtain octachlorocyclopentene, washing the mixed gas extracted under reduced pressure with saturated salt solution, drying and then introducing the mixed gas into the chlorination tower again for reaction;
performing fluorination reaction, namely performing gas-phase fluorine-chlorine exchange reaction on the gasified octafluorocyclopentene and anhydrous hydrogen fluoride serving as raw materials in a fluidized bed reactor under the action of a bismuth-molybdenum co-doped fluorinating agent to generate octafluorocyclopentene; the gasification temperature of the octachlorocyclopentene is 300-350 ℃; the reaction temperature in the fluidized bed reactor is 350-450 ℃, and the reaction pressure is 0.05-0.5 MPa; rectifying the product after reaction to obtain octafluorocyclopentene,
the bismuth-molybdenum co-doped fluorinating agent is prepared according to the following scheme:
according to the mass portion, 8-13 portions of ammonium hexafluoroaluminate micro powder, 0.1-2 portions of ammonium tetrathiomolybdate, 0.5-2 portions of solid binder nano zirconium dioxide, 0.05-0.8 portion of perfluoroalkyl silyl mica, 0.8-2.7 portions of pore-forming agent ethyl cellulose, 2-5 portions of ferric trichloride and 0.01-0.3 portion of bismuth nitrate are added into a ball milling tank, after being uniformly mixed, 35-55 portions of terpineol and 80-120 portions of ethanol are added, 0.01-0.3 portion of gadolinium silver tungstate is then ball milled for 24-36h, after the ball milling is completed, the ethanol is evaporated, the obtained slurry is prepared into microspheres with the particle size of 0.05-0.5mm on a granulator, and is dried for 20-30min at the temperature of 70-90 ℃ to obtain dried microsphere particles, then the dried microsphere particles are calcined for 1-5h at the temperature of 400 ℃, mixed gas of nitrogen and hydrogen fluoride is introduced to fluorinate at the temperature of 300-350 ℃, thus obtaining the bismuth-molybdenum codoped fluorinating agent.
2. The continuous industrial preparation method of octafluorocyclopentene according to claim 1, characterized in that: in the chlorination reaction, the residence time of the mixed gas in the first area of the chlorination tower is 3-8min, the residence time in the second area is 5-10min, the residence time in the third area is 8-12min, and the residence time in the fourth area is 8-15 min.
3. The continuous industrial preparation method of octafluorocyclopentene according to claim 1, characterized in that: the contact time of the fluorination reaction in the reaction bed is 10-30 s.
4. The continuous industrial preparation method of octafluorocyclopentene according to claim 1, characterized in that: the molar ratio of anhydrous hydrogen fluoride to octachlorocyclopentene in the fluorination reaction is 8-12: 1.
5. The continuous industrial preparation method of octafluorocyclopentene according to claim 1, characterized in that: the volume ratio of the mixed gas of the nitrogen and the hydrogen fluoride is 1: 0.5-3.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998055429A1 (en) * | 1997-06-05 | 1998-12-10 | F2 Chemicals Ltd. | Solvents for use in fluorination reactions |
| CN1270575A (en) * | 1997-09-17 | 2000-10-18 | 森陶硝子株式会社 | Method for producing perhalogenated cyclopentene |
| CN107188778A (en) * | 2017-05-18 | 2017-09-22 | 北京宇极科技发展有限公司 | The preparation method of octafluoro cyclopentene |
| CN108164390A (en) * | 2017-12-20 | 2018-06-15 | 大连九信精细化工有限公司 | A kind of industrialized preparing process of perfluoro-cyclopentene |
| CN108276243A (en) * | 2017-12-20 | 2018-07-13 | 大连九信精细化工有限公司 | A kind of industrialized preparing process of octafluoro cyclopentene |
-
2019
- 2019-08-29 CN CN201910810820.XA patent/CN110563545B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998055429A1 (en) * | 1997-06-05 | 1998-12-10 | F2 Chemicals Ltd. | Solvents for use in fluorination reactions |
| CN1270575A (en) * | 1997-09-17 | 2000-10-18 | 森陶硝子株式会社 | Method for producing perhalogenated cyclopentene |
| CN107188778A (en) * | 2017-05-18 | 2017-09-22 | 北京宇极科技发展有限公司 | The preparation method of octafluoro cyclopentene |
| CN108164390A (en) * | 2017-12-20 | 2018-06-15 | 大连九信精细化工有限公司 | A kind of industrialized preparing process of perfluoro-cyclopentene |
| CN108276243A (en) * | 2017-12-20 | 2018-07-13 | 大连九信精细化工有限公司 | A kind of industrialized preparing process of octafluoro cyclopentene |
Non-Patent Citations (2)
| Title |
|---|
| 八氟环戊烯的制备;徐卫国;《有机氟工业》;20061231(第2期);第24-25页 * |
| 新型含氟电子气体八氟环戊烯的合成方法及应用;徐娇 等;《有机氟工业》;20131231(第4期);第13-18页 * |
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