CN115231993B - Method for preparing hexafluoroacetone from hexafluoropropylene oxide - Google Patents
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- CN115231993B CN115231993B CN202211161399.2A CN202211161399A CN115231993B CN 115231993 B CN115231993 B CN 115231993B CN 202211161399 A CN202211161399 A CN 202211161399A CN 115231993 B CN115231993 B CN 115231993B
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- hexafluoropropylene oxide
- hexafluoroacetone
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- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 title claims abstract description 89
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 144
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- 238000006317 isomerization reaction Methods 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 18
- 150000004706 metal oxides Chemical class 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000003682 fluorination reaction Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 22
- 238000012856 packing Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- DAFIBNSJXIGBQB-UHFFFAOYSA-N perfluoroisobutene Chemical group FC(F)=C(C(F)(F)F)C(F)(F)F DAFIBNSJXIGBQB-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BKWAVXQSZLEURV-UHFFFAOYSA-N 2-chloro-1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)C(Cl)C(F)(F)F BKWAVXQSZLEURV-UHFFFAOYSA-N 0.000 description 1
- HBAHZZVIEFRTEY-UHFFFAOYSA-N 2-heptylcyclohex-2-en-1-one Chemical compound CCCCCCCC1=CCCCC1=O HBAHZZVIEFRTEY-UHFFFAOYSA-N 0.000 description 1
- DOJXGHGHTWFZHK-UHFFFAOYSA-N Hexachloroacetone Chemical compound ClC(Cl)(Cl)C(=O)C(Cl)(Cl)Cl DOJXGHGHTWFZHK-UHFFFAOYSA-N 0.000 description 1
- 229920001367 Merrifield resin Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/864—Cobalt and 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and 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
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- 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
Abstract
The invention belongs to the technical field of organic fluorine chemical synthesis, and particularly relates to a method for preparing hexafluoroacetone from hexafluoropropylene oxide. The process comprises contacting a hexafluoropropylene oxide feed stream with a first amount of a catalyst to produce hexafluoroacetone, wherein the first product stream comprises unreacted hexafluoropropylene oxide and produced hexafluoroacetone; contacting the first product stream with a second amount of catalyst to produce hexafluoroacetone, wherein the second product stream comprises residual unreacted hexafluoropropylene oxide and produced hexafluoroacetone; contacting the second product stream with a third amount of catalyst to convert unreacted hexafluoropropylene oxide therein to hexafluoroacetone. The method has mild reaction conditions, realizes the stable operation of catalytic reaction under low temperature, and has high hexafluoropropylene oxide conversion rate and hexafluoroacetone selectivity.
Description
Technical Field
The invention belongs to the technical field of organic fluorine chemical synthesis, and particularly relates to a method for preparing hexafluoroacetone from hexafluoropropylene oxide.
Background
Hexafluoroacetone (HFA) is widely used as a fluorine-containing fine chemical and is also an important raw material intermediate in the organic fluorine industry, and is widely applied to the fields of coatings, medicines, pesticides, high polymers, new materials for microelectronics and the like. Originally produced by Du Pont corporation in the United states and Daikin corporation in Japan. Due to the fact that the molecule has two strong electron-withdrawing groups-CF 3 Group ofThe hexafluoroacetone obtained has unique physicochemical properties and application value.
At present, the preparation method of hexafluoroacetone mainly comprises five methods:
(1) The octafluoroisobutylene oxidation method, because of the high toxicity of octafluoroisobutylene, needs to dissolve it in methanol first to get methanol absorption liquid of octafluoroisobutylene, prepare hexafluoroacetone by oxidizing, this method technical requirement is high, and the raw materials are toxic greatly, is not suitable for the large-scale production application;
(2) The hexafluoropropylene catalytic oxidation method uses oxides of aluminum, iron and the like as catalysts, and has the defects of low product yield;
(3) The 2-chlorohexafluoropropane oxidation method is adopted, the reaction is carried out under the catalysis of ultraviolet light, and the product yield is low;
(4) The gas phase fluorination method of hexachloroacetone has more byproducts and difficult separation;
(5) Hexafluoropropylene oxide (HFPO) isomerization, which is currently the major process for the industrial production of hexafluoroacetone, a highly active, highly selective and stable catalyst is a key factor affecting industrial applications.
For example, patent US20040186322A1 uses TiO 2 Or fluorinated TiO 2 As isomerization catalysts. At 190 ℃, the conversion rate of the hexafluoropropylene oxide of 100 percent and the selectivity of the hexafluoroacetone of more than 99 percent can be obtained. When the temperature was reduced to 60 ℃, the conversion rate was reduced to 80%. Higher reaction temperatures tend to affect catalyst stability.
The patent US3321515 describes the use of Al 2 O 3 、AlBr 3 、AlCl 3 、SnCl 4 、TiO 2 、WO 2 The catalyst for producing hexafluoroacetone by isomerizing hexafluoropropylene oxide was examined by gas-phase and liquid-phase reactions, but the reaction conversion and the yield of hexafluoroacetone were low. US4238416 uses fluorinated Al 2 O 3 Or Al 2 O 3 -SiO 2 As an isomerization reaction catalyst, high hexafluoropropylene oxide conversion rate and hexafluoroacetone selectivity can be obtained, but the reaction temperature is high, the reaction is required to be carried out at 100 to 200 ℃, and the reaction is required to be carried outNitrogen and oxygen were introduced.
In patent CN111004099a, substituted phenol condensed by Merrifield resin loaded on activated carbon is used as a catalyst, liquid phase catalysis is performed to isomerize hexafluoropropylene oxide to prepare hexafluoroacetone, the yield of hexafluoroacetone is about 96%, but hexafluoroacetone prepared by liquid phase reaction needs to be separated by distillation, and the operation flow is complex.
Therefore, a method for preparing hexafluoroacetone by isomerizing hexafluoropropylene oxide with high conversion rate and high selectivity under mild conditions of low temperature and normal pressure is needed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for preparing the hexafluoroacetone from the hexafluoropropylene oxide has mild reaction conditions, realizes stable operation of catalytic reaction under low temperature conditions, has high hexafluoropropylene oxide conversion rate and hexafluoroacetone selectivity, and is suitable for industrial production.
A method for preparing hexafluoroacetone from hexafluoropropylene oxide comprises the following steps:
(1) A first reaction stage: contacting a hexafluoropropylene oxide feed stream with a first amount of an isomerization catalyst to effect an isomerization reaction to convert hexafluoropropylene oxide to hexafluoroacetone at a first conversion to produce a first product stream comprising hexafluoroacetone and unreacted hexafluoropropylene oxide;
(2) And a second reaction stage: contacting the first product stream with a second amount of an isomerization catalyst to effect isomerization and to convert unreacted hexafluoropropylene oxide in the first product stream to hexafluoroacetone at a second conversion rate to produce a second product stream comprising hexafluoroacetone and remaining unreacted hexafluoropropylene oxide;
(3) A third reaction stage: contacting the second product stream with a third amount of an isomerization catalyst to effect isomerization and to convert unreacted hexafluoropropylene oxide in the second product stream to hexafluoroacetone at a third conversion rate to produce a final product stream comprising hexafluoroacetone.
In the present invention, the third amount of isomerization catalyst is greater than the second amount of isomerization catalyst, which is greater than the first amount of isomerization catalyst.
In the invention, the contact time of the hexafluoropropylene oxide feed stream and the first amount of the isomerization reaction catalyst is 2 to 8s, the contact time of the first product stream and the second amount of the isomerization reaction catalyst is 10 to 25s, and the contact time of the second product stream and the third amount of the isomerization reaction catalyst is 25 to 40s.
In the invention, the isomerization reaction catalyst is a Cr-based composite metal oxide modified by one of fluorinated Fe, co and Ni.
One Cr-based composite metal oxide modified by Fe, co and Ni is recorded as: nwt% M x O y -Cr 2 O 3 ;
Wherein M is one of Fe, co and Ni; m x O y NiO and Fe 2 O 3 One of CoO and CoO; n is an active component M x O y The mass fraction of the catalyst is preferably 5 to 30, and more preferably 10 to 20.
Preferably, the Cr-based composite metal oxide modified by one of Fe, co and Ni is prepared by a precipitation method, and the preparation process comprises the following steps:
weighing soluble salts of the active component M and chromium, adding deionized water, stirring for dissolving, dropwise adding ammonia water into the solution under stirring until the precipitate is completely precipitated, aging, washing, separating, drying the precipitate in a drying oven at 120 ℃, and roasting in a muffle furnace at 400 ℃ for 6 hours.
Preferably, during the fluorination of the Cr-based composite metal oxide modified by one of Fe, co and Ni, inert gas is firstly used for purging, drying is carried out, and then mixed gas flow of nitrogen and HF is used for purging, so that the fluorination is carried out.
Further preferably, the Cr-based composite metal oxide modified with one of Fe, co, and Ni is purged at 200 to 350 ℃ with an inert gas (e.g., nitrogen, argon, etc.) during drying; and blowing the dried Cr-based composite metal oxide modified by one of Fe, co and Ni by using mixed gas flow of nitrogen and HF at the temperature of 200-350 ℃ during activation, wherein the nitrogen accounts for 10-35% of the total gas volume, and finally blowing and cooling to room temperature by using excessive nitrogen.
In the present invention, the isomerization reaction temperature is 0 to 50 ℃, preferably 20 to 40 ℃.
In the present invention, the isomerization reaction is not critical in terms of pressure, and the reaction may be carried out at atmospheric pressure, below or above atmospheric pressure.
In the invention, the conversion rate of hexafluoropropylene oxide is controlled to be 40 to 60 percent in the first reaction stage; controlling the conversion rate of hexafluoropropylene oxide to be 50-80% in the second reaction stage; in the third reaction stage, the conversion rate of hexafluoropropylene oxide is controlled to be 80-100%; wherein the conversion rate of the hexafluoropropylene oxide in the first reaction stage is less than the conversion rate of the hexafluoropropylene oxide in the second reaction stage, and the conversion rate of the hexafluoropropylene oxide in the second reaction stage is less than the conversion rate of the hexafluoropropylene oxide in the third reaction stage.
The three stage reaction described above may include more than three reaction stages, such as four or five or more, if not sufficient to achieve the desired hexafluoropropylene oxide conversion and hexafluoroacetone selectivity during the isomerization reaction. The reaction stages can be carried out at different locations in the same reactor or in a plurality of different reactors.
The reaction formula for preparing hexafluoroacetone by isomerizing hexafluoropropylene oxide is as follows:
compared with the prior art, the invention has the following beneficial effects:
(1) In the reaction process of preparing the hexafluoroacetone by isomerizing the hexafluoropropylene oxide, the invention realizes the complete conversion of the hexafluoroacetone, and the hexafluoroacetone has high selectivity;
(2) The isomerization reaction can be carried out under mild conditions of low temperature and normal pressure, the flow operation is simple, the whole reaction flow is carried out by stages, the overhigh temperature of a catalyst bed layer caused by reaction heat release can be effectively avoided, the stable operation of the catalyst is ensured, and meanwhile, the preparation process of the catalyst used in the reaction is simple, and the large-scale industrial production is easy.
Drawings
FIG. 1 is a reaction process flow diagram according to one embodiment of the present invention comprising one reactor;
FIG. 2 is a reaction process flow diagram of one embodiment according to the present invention comprising three reactors.
Detailed Description
The present invention will be further described with reference to the following examples.
One embodiment of the invention described with respect to fig. 1 and 2 comprises passing hexafluoropropylene oxide feed stream 0 into the reactor. The feed stream is first subjected to a first stage reaction over a first amount of catalyst a to convert hexafluoropropylene oxide to hexafluoroacetone at a first conversion rate, producing a first product stream 1 comprising hexafluoroacetone and unreacted hexafluoropropylene oxide; the first product stream 1 is further subjected to a second stage reaction over a second amount of catalyst B to convert hexafluoropropylene oxide to hexafluoroacetone at a second conversion rate, producing a second product stream 2 comprising hexafluoroacetone and unreacted hexafluoropropylene oxide; the second product stream 2 is then subjected to a third stage reaction with a third amount of catalyst C to convert hexafluoropropylene oxide to hexafluoroacetone at a third conversion rate, ultimately producing a third product stream 3. The overall reaction scheme is a heterogeneous catalytic reaction that is carried out in a continuous manner.
The hexafluoropropylene oxide conversion and hexafluoroacetone selectivity of the overall reaction can be obtained at relatively high levels through at least three reaction stages. Wherein the first reaction stage is conducted under conditions effective to achieve a relatively low first conversion of the hexafluoropropylene oxide ring, producing a first product stream. The second reaction stage is fed by the first product stream to convert unreacted hexafluoropropylene oxide in the first product stream to hexafluoroacetone at a second conversion rate. The third reaction stage is fed by the second product stream to convert unreacted hexafluoropropylene oxide in the second product stream to hexafluoroacetone at a third conversion rate.
Maintaining a low hexafluoropropylene oxide conversion in the first reaction stage has a significant effect on the selectivity of the hexafluoroacetone produced. Through controlling the raw material feeding amount and the catalyst using amount, the hexafluoropropylene oxide feeding amount is controlled to be sent into the first reaction stage at a speed which is larger than the catalyst production capacity in the first stage, the excessive hexafluoropropylene oxide can take away heat generated in the reaction, and the problem that the catalyst stability is influenced due to overhigh temperature is effectively avoided. In a preferred embodiment, hexafluoropropylene oxide is controlled at 40 to 60% conversion. By controlling the hexafluoropropylene oxide conversion in the first reaction stage, a higher proportion of the reacted hexafluoropropylene oxide can be isomerized to hexafluoroacetone in the first reaction stage, with a selectivity to hexafluoroacetone of at least 90%, preferably at least 95%, and more preferably at least 99% being produced in many embodiments.
The first product stream from the first reaction stage is passed directly to the second reaction stage where unreacted hexafluoropropylene oxide in the first product stream is isomerized to hexafluoroacetone. It is preferred to efficiently supply hexafluoropropylene oxide into the second reaction stage at a conversion rate higher than the percentage of conversion of hexafluoropropylene oxide in the first reaction stage, with the reaction conversion rate preferably being 50 to 80% operating in the second reaction stage. The second product stream from the second reaction stage is passed directly to the third reaction stage where unreacted hexafluoropropylene oxide in the second product stream is isomerized to hexafluoroacetone. It is preferable that hexafluoropropylene oxide entering into the third reaction stage is efficiently supplied at a conversion rate higher than the conversion rate of hexafluoropropylene oxide in the second reaction stage, and the reaction conversion rate is preferably 80 to 100% in operating the third reaction stage. In many embodiments it is preferred that the selectivity to hexafluoroacetone produced in the second and third reaction stages be at least 90%, preferably at least 95%, more preferably at least 99%.
The reaction in each stage is carried out by adjusting the contact time of the feed and the catalyst by adjusting the amounts of the catalyst and the inert porous filler so that the reaction conversion and the product selectivity in each reaction stage are controlled within the above-specified ranges. Wherein the contact time of the hexafluoropropylene oxide feed stream 0 and the first amount of the catalyst A is 2 to 8s, the contact time of the first product stream 1 and the second amount of the catalyst B is 10 to 25s, and the contact time of the second product stream 2 and the third amount of the catalyst C is 25 to 40s.
However, if this three stage reaction scheme is insufficient to produce the desired hexafluoropropylene oxide conversion and hexafluoroacetone selectivity, the overall reaction scheme may include more than three reaction stages, such as 4 stages or 5 stages or more.
The preferred isomerization catalyst in many embodiments is a fluorinated Cr-based composite metal oxide modified with one of Fe, co, and Ni.
Fe. One of the Cr-based composite metal oxides modified by Co and Ni is recorded as: nwt% M x O y -Cr 2 O 3 ;
Wherein M is one of Fe, co and Ni; m x O y NiO and Fe 2 O 3 And CoO; n is an active component M x O y The mass fraction of the catalyst is preferably 5 to 30, more preferably 10 to 20.
Fe. The Cr-based composite metal oxide modified by one of Co and Ni is prepared by a precipitation method, and the preparation process comprises the following steps:
weighing soluble salts of the active component M and chromium, adding deionized water, stirring for dissolving, dropwise adding ammonia water into the solution under stirring until the precipitate is completely precipitated, aging, washing, separating, drying the precipitate in a drying oven at 120 ℃, and roasting in a muffle furnace at 400 ℃ for 6 hours.
Preferably, in the fluorination of the Cr-based composite metal oxide modified by one of Fe, co and Ni, purging with an inert gas is performed, drying is performed, and then purging with a mixed gas flow of nitrogen and HF is performed to perform fluorination.
Further preferably, the Cr-based composite metal oxide modified with one of Fe, co, and Ni is purged at 200 to 350 ℃ with an inert gas (e.g., nitrogen, argon, etc.) during drying; and blowing the dried Cr-based composite metal oxide modified by one of Fe, co and Ni by using mixed gas flow of nitrogen and HF at the temperature of 200 to 350 ℃ during activation, wherein the nitrogen accounts for 10 to 35 percent of the total gas volume, and finally blowing and cooling to the room temperature by using excessive nitrogen.
The catalyst preparation method in the examples is as follows:
weighing a certain amount of soluble salts of metal M and chromium according to a proportion, adding deionized water, stirring and dissolving, dropwise adding ammonia water into the prepared solution in the stirring process, keeping the pH value at 8.0 +/-0.5 until the precipitation is complete, then aging, washing and separating, drying in a 120 ℃ oven, roasting in a muffle furnace at 400 ℃ for 6h, naturally cooling to room temperature, and tabletting and forming to obtain metal M modified chromium oxide; by adjusting the amount of M salt added, nwt% M with different compositions can be obtained x O y -Cr 2 O 3 A composite metal oxide.
Placing 100ml of the prepared composite metal oxide in a tubular fixed bed reactor, and placing N at 300 DEG C 2 After purging for 5h, HF and N were introduced 2 Purging the mixed gas at 300 ℃ for 8h, wherein the flow rate of the mixed gas is 1000ml/min, and HF and N are 2 4:1, finally in N 2 Blowing and reducing the temperature to room temperature to obtain the fluorinated nwt percent M x O y -Cr 2 O 3 Catalyst, noted nwt% M x O y -Cr 2 O 3 (F)。
Evaluation of catalyst:
the reaction is carried out in a tubular fixed bed reactor, the reaction system comprising one or more reaction tubes connected in series. The straight tube reactor has the size of De 25X 2.5mm and the length of 100cm. The raw materials are accurately regulated by a mass flow meter and enter the reactor. The product was calculated by gas chromatography analysis.
Example 1
In a reaction system comprising one reactor (as shown in fig. 1), hexafluoropropylene oxide was introduced into a straight tube reactor packed with a different catalyst. The catalyst volume is 30ml, the hexafluoropropylene oxide feed rate is 100ml/min, the reaction is carried out for 24h at normal temperature (20 ℃) and normal pressure, and the catalytic reaction performance results are shown in Table 1.
Filling a catalyst:
a first section: 4ml of catalyst, the contact time of the feed with the catalyst being 2.4s;
a second section: 10ml of catalyst with 25ml of inert porous packing, the contact time of the feed with the catalyst being 21s;
a third section: 16ml of catalyst with 40ml of inert porous packing, the contact time of the feed with the catalyst was 32s.
The first section, the second section and the third section are respectively positioned at the upper part, the middle part and the lower part of the reaction tube, and each section is separated by inert porous packing. The catalyst filled in the second section and the third section is doped and uniformly mixed by inert porous filler.
TABLE 1
Example 2
In a reaction system comprising three reactors (as shown in fig. 2), the reaction is carried out in a reaction system comprising three reactors in series, and hexafluoropropylene oxide is introduced into the reaction system. The catalyst volume is 80ml, the hexafluoropropylene oxide feed rate is 300ml/min, the reaction is carried out for 24h at normal temperature (20 ℃) and normal pressure. The catalytic performance results are shown in table 2.
Filling a catalyst:
a first section: 10ml of catalyst with 20ml of inert porous packing, the contact time of the feed with the catalyst being 6s;
a second section: 28ml of catalyst with 25ml of inert porous packing, the contact time of the feed with the catalyst being 16s;
a third section: 42ml of catalyst with 40ml of inert porous packing and a contact time of feed with catalyst of 21s.
The first section, the second section and the third section are respectively positioned in the three reaction tubes. The catalysts filled in the first section, the second section and the third section are doped and uniformly mixed by inert porous fillers.
Example 3
In a reaction system comprising three reactors (as shown in fig. 2), the reaction is carried out in a reaction system comprising three reactors in series, and hexafluoropropylene oxide is introduced into the reaction system. The catalyst volume is 80ml, the hexafluoropropylene oxide feed rate is 300ml/min, the reaction is carried out for 24h at normal temperature (20 ℃) and normal pressure. The catalytic performance results are shown in table 2.
Filling a catalyst:
a first section: 10ml of catalyst, the contact time of the feed with the catalyst being 2s;
a second section: 25ml of catalyst with 25ml of inert porous packing, the contact time of the feed with the catalyst being 10s;
a third section: 45 ml catalyst with 80ml inert porous packing and contact time of feed and catalyst of 25s.
The first section, the second section and the third section are respectively positioned in the three reaction tubes. The catalysts filled in the first section, the second section and the third section are doped and uniformly mixed by inert porous fillers.
Example 4
In a reaction system comprising three reactors (as shown in fig. 2), the reaction is carried out in a reaction system comprising three reactors in series, and hexafluoropropylene oxide is introduced into the reaction system. The catalyst volume is 80ml, the hexafluoropropylene oxide feed rate is 300ml/min, the reaction is carried out for 24h at normal temperature (20 ℃) and normal pressure. The catalytic performance results are shown in table 2.
Filling a catalyst:
a first section: 15 ml of catalyst with 25ml of inert porous packing, the contact time of the feed with the catalyst being 8s;
a second section: 30ml of catalyst with 95ml of inert porous packing, the contact time of the feed with the catalyst being 25s;
a third section: 35 ml catalyst with 165ml inert porous packing and contact time of feed and catalyst was 40s.
The first section, the second section and the third section are respectively positioned in the three reaction tubes. The catalysts filled in the first section, the second section and the third section are doped and uniformly mixed by inert porous fillers.
TABLE 2
Example 5
Reaction conditions were the same as in example 2, for 10wt% CoO-Cr 2 O 3 (F) The stability of the catalyst in the isomerization of hexafluoropropylene oxide was investigated. The catalytic performance results are shown in table 3.
TABLE 3
Comparative example 1
In a reaction system comprising one reactor, hexafluoropropylene oxide is introduced into a reactor directly charged with Cr 2 O 3 (F) In a straight tube reactor for the catalyst. The catalyst volume is 30ml, the hexafluoropropylene oxide feed rate is 100ml/min, the reaction is carried out at normal temperature (20 ℃) and normal pressure.
By the time of 80h of reaction, the catalyst bed temperature had risen from room temperature to 78.2 ℃, and as the reaction continued, the hexafluoropropylene oxide conversion and hexafluoroacetone selectivity began to decline.
Claims (3)
1. A method for preparing hexafluoroacetone from hexafluoropropylene oxide is characterized in that: the method comprises the following steps:
(1) A first reaction stage: contacting a hexafluoropropylene oxide feed stream with a first amount of an isomerization catalyst to effect an isomerization reaction to convert hexafluoropropylene oxide to hexafluoroacetone at a first conversion rate to produce a first product stream comprising hexafluoroacetone and unreacted hexafluoropropylene oxide;
(2) And a second reaction stage: contacting the first product stream with a second amount of an isomerization catalyst to effect isomerization and to convert unreacted hexafluoropropylene oxide in the first product stream to hexafluoroacetone at a second conversion rate to produce a second product stream comprising hexafluoroacetone and remaining unreacted hexafluoropropylene oxide;
(3) A third reaction stage: contacting the second product stream with a third amount of an isomerization catalyst to effect isomerization and to convert unreacted hexafluoropropylene oxide in the second product stream to hexafluoroacetone at a third conversion rate to produce a final product stream comprising hexafluoroacetone;
wherein the third amount of isomerization catalyst is greater than the second amount of isomerization catalyst, which is greater than the first amount of isomerization catalyst;
the contact time of the hexafluoropropylene oxide feed stream and the first amount of the isomerization reaction catalyst is 2 to 8s, the contact time of the first product stream and the second amount of the isomerization reaction catalyst is 10 to 25s, and the contact time of the second product stream and the third amount of the isomerization reaction catalyst is 25 to 40s;
the isomerization reaction temperature is 20 to 40 ℃;
the isomerization reaction catalyst is a Cr-based composite metal oxide modified by one of fluorinated Fe, co and Ni;
one Cr-based composite metal oxide modified by Fe, co and Ni is recorded as: nwt% M x O y -Cr 2 O 3 ;
Wherein M is one of Fe, co and Ni; m x O y NiO and Fe 2 O 3 One of CoO and CoO; n is an active component M x O y Accounts for the mass fraction of the catalyst, and the value of n is 5 to 30;
the Cr-based composite metal oxide modified by one of Fe, co and Ni is prepared by a precipitation method;
when the Cr-based composite metal oxide modified by one of Fe, co and Ni is fluorinated, inert gas is firstly adopted for purging, drying is carried out, and then mixed gas flow of nitrogen and HF is adopted for purging, so that fluorination is carried out.
2. The process for producing hexafluoroacetone from hexafluoropropylene oxide as claimed in claim 1, wherein: the conversion rate of hexafluoropropylene oxide is controlled to be 40-60% in the first reaction stage; in the second reaction stage, the conversion rate of hexafluoropropylene oxide is controlled to be 50-80%; in the third reaction stage, the conversion rate of hexafluoropropylene oxide is controlled to be 80-100%; wherein the conversion rate of the hexafluoropropylene oxide in the first reaction stage is less than the conversion rate of the hexafluoropropylene oxide in the second reaction stage, and the conversion rate of the hexafluoropropylene oxide in the second reaction stage is less than the conversion rate of the hexafluoropropylene oxide in the third reaction stage.
3. The process for producing hexafluoroacetone from hexafluoropropylene oxide as claimed in claim 1, wherein: the reaction stages are carried out at different locations in the same reactor or in a plurality of different reactors.
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