CN111362887A - Method for preparing hexafluoropropylene oxide by catalytic oxidation - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention belongs to the field of catalysts, and particularly relates to a method for preparing hexafluoropropylene oxide by catalytic oxidation, which comprises the following steps: 1) preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide CTAB in distilled water, and sequentially adding ammonia water and tetraethoxysilane TEOS into the solution; continuously adding a cesium fluoride solution and a silver nitrate solution; adding the mixture into a reaction kettle containing a polytetrafluoroethylene lining, crystallizing, taking out a sample, performing suction filtration washing, drying, and roasting at a high temperature in a muffle furnace to prepare the catalyst; 2) preparing the catalyst calcined in the step 1) into catalyst particles of 40-60 meshes, loading the catalyst particles into a tubular reactor, and heating; and then sequentially introducing hexafluoropropylene and oxygen into the tubular reactor, and collecting a reaction product. The reaction for generating the hexafluoropropylene oxide by using the hexafluoropropylene conversion of the invention is carried out in gas phase, the reaction speed is high, the reaction temperature is low, the conversion rate and the selectivity are high, and the operation is simple and safe.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a method for preparing hexafluoropropylene oxide by catalytic oxidation.
Background
Hexafluoropropylene oxide, also known as perfluoropropylene oxide, was first reported by DuPont in the 60 th 20 th century to synthesize hexafluoropropylene oxide, is an important intermediate in the field of organic fluorine chemistry, and is a basic raw material for synthesizing various fluorine-containing functional compounds, such as perfluoropropionyl fluoride, hexafluoroacetone, perfluoroalkyl vinyl ether, perfluoropolyether, and the like. Therefore, how to economically and efficiently synthesize hexafluoropropylene oxide is an important research topic of fluorine chemical industry, because it can directly reduce the cost of various fluorine-containing functional compounds and expand the application field thereof. Synthesis of hexafluoropropylene oxide is essentially hexafluoropropylene oxide produced, and this conversion can be accomplished by a variety of oxidants during the reaction. At present, hexafluoropropylene oxide is synthesized from hexafluoropropylene, mainly using a liquid type oxidant and oxygen. The liquid oxidant mainly comprises hydrogen peroxide and sodium hypochlorite solution, although the liquid oxidant can obtain high conversion rate and selectivity when used for synthesizing hexafluoropropylene oxide, and particularly sodium hypochlorite is used as the oxidant. In patent CN1049661, a toluene-sodium hypochlorite-hexafluoropropylene three-liquid phase system is adopted in a high pressure reaction kettle, and the reaction can obtain 56% conversion rate and 81% selectivity at most. In recent years, in patent US20120016142, a micro pipeline reactor is adopted, the conversion rate of the reaction can reach 70%, the selectivity can reach 99%, but hydrogen peroxide or sodium hypochlorite is adopted as an oxidant, the price is expensive relative to oxygen, the reaction is carried out in a reaction kettle, higher pressure is required, and not only the processes use a large amount of organic solvents, but also a large amount of waste water is generated after the reaction, and the cost for synthesizing the hexafluoropropylene oxide by using the method is increased due to huge waste water treatment cost.
The preparation of hexafluoropropylene oxide by using oxygen as oxidant can be divided into oxygen liquid phase oxidation and oxygen gas phase catalytic oxidation according to different preparation processes.
The oxygen liquid phase oxidation method is that hexafluoropropylene, oxygen and solvent are added into a reaction kettle to synthesize hexafluoropropylene oxide under the conditions of high temperature and high pressure. In patent US3536733, CFC-113 was used as solvent, and in an autoclave, a conversion of 70% and a selectivity of 70% were obtained. The method needs to use a large amount of environmentally-friendly fluorine-containing solvent CFC-113 which can destroy the ozone layer in the synthetic process, and is forbidden to be used by a plurality of countries at present. In recent years, although CFC-113 alternative solvent is used in the reaction process, for example, in patent CN1634902, HFE-227e is used as the reaction solvent, the solvent still has high GWP value, which can cause greenhouse effect and global warming. Moreover, the oxygen liquid phase oxidation process needs to be carried out at high temperature and high pressure, which has high requirements for reaction equipment and also has the danger of explosion caused by instantaneous and violent exothermic reaction. In addition, the oxygen liquid phase oxidation method generally adopts a batch production mode, and the utilization rate of reaction equipment is low.
The oxygen gas phase catalytic oxidation method is that a tubular reactor is filled with a solid phase catalyst with a certain particle size, then the catalyst is heated to a specified temperature, and hexafluoropropylene and oxygen pass through a catalyst bed layer to react on the surface of the catalyst to obtain hexafluoropropylene oxide. The method has the advantages that no fluorine-containing solvent is needed in the synthesis process, the reaction is only carried out under normal pressure or low pressure, the reaction process is continuous, and the equipment utilization rate is high. In patents US3775438 and US3775439, dupont uses silica gel as catalyst, in the hexafluoropropylene oxygen oxidation experiment, hexafluoropropylene obtained 45% conversion, hexafluoropropylene oxide selectivity reached 73%. In patent US4288376, the japanese dajin company uses barium compounds as catalyst and hexafluoropropylene achieves a conversion of up to 40% and a selectivity of 70%. In patent US5210866, a conversion of 46% and a selectivity of 75% were obtained in an experiment for the preparation of hexafluoropropylene oxide using silica as carrier, bentonite as modifier and copper oxide as catalyst.
However, in the conventional oxygen gas phase catalytic oxidation method, the preparation process of the catalyst required for the reaction is complicated, and the loading and calcination of the active component and the modifier are required to be performed in a plurality of steps. In addition, because the catalyst needs to be impregnated in multiple steps, the carrier, the active component and the modifier are difficult to be uniformly dispersed, the specific surface area of the carrier material used for reaction is small, and the conversion rate of the reaction is lower compared with an oxygen liquid phase oxidation method.
Disclosure of Invention
The invention aims to provide a method for preparing hexafluoropropylene oxide by catalytic oxidation.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing hexafluoropropylene oxide by catalytic oxidation comprises the following steps: 1) preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide CTAB in distilled water, stirring at room temperature, and then sequentially adding ammonia water and tetraethoxysilane TEOS into the solution; continuously adding the cesium fluoride solution and the silver nitrate solution and stirring at room temperature; adding the mixture into a reaction kettle containing a polytetrafluoroethylene lining, after crystallization, taking out a sample, carrying out suction filtration washing, drying, roasting at high temperature in a muffle furnace, pressing the roasted powder for 0.5-5 min at 10-20MPa by using a tablet machine, forming the tablet, crushing the tablet by using a grinding bowl, screening, and selecting particles of 40-60 meshes to obtain the prepared catalyst particles;
2) loading the catalyst particles of 40-60 meshes obtained in the step 1) into a tubular reactor, and heating; and then sequentially introducing hexafluoropropylene and oxygen into the tubular reactor, collecting reaction products, and measuring the conversion rate and the selectivity of the reaction by gas chromatography.
Specifically, the molar ratio of each component in the step 1) is as follows: TEOS: CTAB: NH 3: H2O ═ 1: 0.15:0.68:43.
Specifically, the catalyst obtained in the step 1) comprises the following components: a mesoporous silica support, cesium fluoride and silver oxide; wherein, the content of cesium fluoride is 5-15% of the mass of the mesoporous silica carrier; the content of silver element in the silver oxide is 2-6% of the mass of the mesoporous silica carrier.
Specifically, the specific surface area of the catalyst obtained in the step 1) is 800-2(ii)/g; the pore diameter is 2.4-3.0 nm.
Specifically, the temperature of the reaction in the step 2) is 100-200 ℃, and the pressure of the reaction is 0-0.4 MPa; the space velocity of the hexafluoropropylene and the catalyst is between 0.25 and 5/h; the mass ratio of the hexafluoropropylene to the oxygen is 5-20: 1.
Specifically, the temperature of the reaction in the step 2) is 120-150 ℃, and the pressure of the reaction is 0.1 MPa; the space velocity of the hexafluoropropylene and the catalyst is 0.8/h, and the mass ratio of the hexafluoropropylene to the oxygen is 7: 1.
Compared with the prior art, the invention has the beneficial effects that:
the reaction for generating the hexafluoropropylene oxide by using the hexafluoropropylene conversion of the invention is carried out in gas phase, the reaction speed is high, the reaction temperature is low, the conversion rate and the selectivity are high, and the operation is simple and safe. In the preparation process of the modified silicon dioxide mesoporous catalyst, the cesium fluoride and the silver oxide directly enter the skeleton structure of the catalyst carrier due to one-step synthesis, so that the uniform distribution of the cesium fluoride and the silver oxide components is ensured; meanwhile, the mesoporous silica molecular sieve with high specific surface area prepared by the template method has the advantages that the modifying agent and the catalyst are uniformly dispersed on the carrier due to the high specific surface area, the agglomeration phenomenon is prevented, and the performance of the catalyst is effectively improved.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.
Examples 1 to 9:
dissolving a certain amount of Cetyl Trimethyl Ammonium Bromide (CTAB) in a certain amount of distilled water, stirring for 30 minutes at room temperature, adding a certain amount of ammonia water, and then adding Tetraethoxysilane (TEOS) to ensure that the molar ratio of each component in the solution is as follows: TEOS: CTAB: NH 3: H2O ═ 1: 0.15:0.68:43. The above solution was stirred again at room temperature for 1 hour, then different cesium fluoride solutions and silver nitrate solutions were added thereto, and different catalysts were prepared by adding different amounts of cesium fluoride and silver nitrate (see table 1). Stirring the mixture for 1 hour at room temperature again, then putting the mixture into a reaction kettle with a polytetrafluoroethylene lining, and crystallizing the mixture for 48 hours at 120 ℃. And taking out the sample, then carrying out suction filtration, washing, drying and roasting in a muffle furnace at 400 ℃ for 6 hours. Pressing the roasted powder for 0.5-5 min at 10-20MPa by using a tablet press to form tablets, crushing the tablets by using a grinding bowl, screening, and selecting particles of 40-60 meshes to obtain the prepared catalyst particles;
the prepared catalyst particles with the size of 40-60 meshes are put into a tubular reactor and heated to the temperature of 120 ℃ and 150 ℃, and the reaction pressure is 0.1 MPa. And then sequentially introducing hexafluoropropylene and oxygen into the tubular reactor, wherein the space velocity of the hexafluoropropylene and the catalyst is 0.8/h, and the mass ratio of the hexafluoropropylene to the oxygen is 7: 1. The reaction products were collected and the conversion and selectivity of the reaction were measured by gas chromatography, and table 1 shows the results for the different examples.
TABLE 1
Comparative examples 1 to 8:
comparative examples 1 to 4;
preparing a catalyst by an impregnation method: weighing a certain amount of cesium fluoride and silver nitrate according to the metal loading amount, adding a certain amount of water, stirring to completely dissolve the cesium fluoride and silver nitrate, soaking a proper amount of dried mesoporous silica (same as examples 2 and 3) in an aqueous solution of the cesium fluoride and silver nitrate, fully stirring to saturate the mesoporous silica, adding a proper amount of ammonia water, and stirring. Then the mixture is put into a 120 ℃ oven to be dried for 2 hours and roasted for 5 hours at 400 ℃ in the air. Tabletting and granulating, and screening 40-60 mesh granules for later use.
The prepared catalyst particles with the size of 40-60 meshes are put into a tubular reactor and heated to the temperature of 120 ℃ and 150 ℃, and the reaction pressure is 0.1 MPa. And then sequentially introducing hexafluoropropylene and oxygen into the tubular reactor, wherein the space velocity of the hexafluoropropylene and the catalyst is 0.8/h, and the mass ratio of the hexafluoropropylene to the oxygen is 7: 1. The reaction products were collected, and the conversion and selectivity of the reaction were measured by gas chromatography, and table 2 shows the results corresponding to the different comparative examples.
TABLE 2
Comparative examples 5 to 8;
an unsupported catalyst: weighing a certain amount of cesium fluoride and silver nitrate according to the mass ratio of the metals, adding a certain amount of water, stirring to completely dissolve the cesium fluoride and the silver nitrate, adding a proper amount of ammonia water, and stirring. Then the mixture is put into a 120 ℃ oven to be dried for 2 hours and roasted for 5 hours at 400 ℃ in the air. Tabletting and granulating, and screening 40-60 mesh granules for later use.
The prepared catalyst particles with the size of 40-60 meshes are put into a tubular reactor and heated to the temperature of 120 ℃ and 150 ℃, and the reaction pressure is 0.1 MPa. And then sequentially introducing hexafluoropropylene and oxygen into the tubular reactor, wherein the space velocity of the hexafluoropropylene and the catalyst is 0.8/h, and the mass ratio of the hexafluoropropylene to the oxygen is 7: 1. The reaction products were collected, and the conversion and selectivity of the reaction were measured by gas chromatography, and table 3 shows the results corresponding to the different comparative examples.
TABLE 3
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (6)
1. The method for preparing hexafluoropropylene oxide by catalytic oxidation is characterized by comprising the following steps: 1) preparation of the catalyst: dissolving cetyl trimethyl ammonium bromide CTAB in distilled water, stirring at room temperature, and then sequentially adding ammonia water and tetraethoxysilane TEOS into the solution; continuously adding the cesium fluoride solution and the silver nitrate solution and stirring at room temperature; adding the mixture into a reaction kettle containing a polytetrafluoroethylene lining, crystallizing, taking out a sample, performing suction filtration washing, drying, and roasting at a high temperature in a muffle furnace to prepare the catalyst;
2) preparing the catalyst calcined in the step 1) into catalyst particles of 40-60 meshes, loading the catalyst particles into a tubular reactor, and heating; and then sequentially introducing hexafluoropropylene and oxygen into the tubular reactor, collecting reaction products, and measuring the conversion rate and the selectivity of the reaction by gas chromatography.
2. The catalytic oxidation process for preparing hexafluoropropylene oxide according to claim 1, wherein the molar ratio of each component in step 1) is: TEOS: CTAB: NH 3: H2O ═ 1: 0.15:0.68:43.
3. The process for preparing hexafluoropropylene oxide by catalytic oxidation according to claim 1, wherein the catalyst obtained in step 1) comprises the following components: a mesoporous silica support, cesium fluoride and silver oxide; wherein, the content of cesium fluoride is 5-15% of the mass of the mesoporous silica carrier; the content of silver element in the silver oxide is 2-6% of the mass of the mesoporous silica carrier.
4. The process for preparing hexafluoropropylene oxide by catalytic oxidation as set forth in claim 1, wherein the specific surface area of the catalyst obtained in step 1) is 800-1000m2(ii)/g; the pore diameter is 2.4-3.0 nm.
5. The process for producing hexafluoropropylene oxide by catalytic oxidation as set forth in claim 1, wherein the temperature of the reaction in the step 2) is 100-; the space velocity of the hexafluoropropylene and the catalyst is between 0.25 and 5/h; the mass ratio of the hexafluoropropylene to the oxygen is 5-20: 1.
6. The process for producing hexafluoropropylene oxide by catalytic oxidation as set forth in claim 1, wherein the temperature of the reaction in the step 2) is 120-; the space velocity of the hexafluoropropylene and the catalyst is 0.8/h, and the mass ratio of the hexafluoropropylene to the oxygen is 7: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112457176A (en) * | 2020-11-25 | 2021-03-09 | 山东华夏神舟新材料有限公司 | Method for continuously producing hexafluoroacetone |
| CN115385873A (en) * | 2022-10-25 | 2022-11-25 | 山东华夏神舟新材料有限公司 | Continuous synthesis method of perfluoro-2, 3-epoxy-2-methylpentane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112457176A (en) * | 2020-11-25 | 2021-03-09 | 山东华夏神舟新材料有限公司 | Method for continuously producing hexafluoroacetone |
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| CN115385873A (en) * | 2022-10-25 | 2022-11-25 | 山东华夏神舟新材料有限公司 | Continuous synthesis method of perfluoro-2, 3-epoxy-2-methylpentane |
| CN115385873B (en) * | 2022-10-25 | 2023-01-03 | 山东华夏神舟新材料有限公司 | Continuous synthesis method of perfluoro-2, 3-epoxy-2-methylpentane |
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