阅读说明：本技术 气相连续制备3,3,3-三氟-2-(三氟甲基)-1-丙烯的方法 (Method for continuously preparing 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene in gas phase ) 是由 张呈平 贾晓卿 董利 权恒道 于 2021-04-08 设计创作，主要内容包括：本发明公开了一种气相连续制备3,3,3-三氟-2-(三氟甲基)-1-丙烯的方法,以八氟异丁烯为原料通过加氢-脱氟化氢-加氢-脱氟化氢四步气相连续反应,得到3,3,3-三氟-2-(三氟甲基)-1-丙烯。本发明的加氢催化剂、脱氟化氢催化剂均具有活性高、使用寿命长的特点；并通过气相独立循环工艺,将反应不完全的物料进行独立循环,可以使初始原料几乎完全地转化3,3,3-三氟-2-(三氟甲基)-1-丙烯,最终从工艺体系中高效率、气相连续循环地采出的是产品3,3,3-三氟-2-(三氟甲基)-1-丙烯,从而不产生液废和废气,实现绿色生产。(The invention discloses a method for continuously preparing 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene in a gas phase, which takes octafluoroisobutylene as a raw material to obtain 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene through four-step gas phase continuous reaction of hydrogenation-dehydrofluorination-hydrogenation-dehydrofluorination. The hydrogenation catalyst and the dehydrofluorination catalyst have the characteristics of high activity and long service life; and the materials which are not completely reacted are independently circulated by a gas-phase independent circulation process, so that the initial raw materials can be almost completely converted into the 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene, and finally the product 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene is continuously and circularly extracted from the gas phase at high efficiency from a process system, thereby not generating liquid waste and waste gas and realizing green production.)

1. A process for the continuous preparation of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene in the gas phase, characterized in that: the method comprises the following steps:

(1) gas-phase hydrogenation reaction I: in the presence of a hydrogenation catalyst, carrying out gas phase addition on octafluoroisobutylene and hydrogen to obtain 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane;

(2) dehydrofluorination reaction I: in the presence of a dehydrofluorination catalyst, 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is used as a raw material to carry out dehydrofluorination reaction to obtain 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propylene;

(3) gas-phase hydrogenation reaction II: in the presence of a hydrogenation catalyst, carrying out gas phase addition on 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propylene and hydrogen to obtain 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane;

(4) dehydrofluorination reaction II: in the presence of a dehydrofluorination catalyst, 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is used as a raw material to carry out dehydrofluorination reaction to obtain 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene;

the hydrogenation catalyst consists of any one of palladium and platinum simple substance and CrF₃、FeF₃、CoF₂、NiF₂、ZnF₂、MgF₂、CaF₂、BaF₂、SrF₂、AlF₃、GaF₃Or InF₃Any one of the carriers, wherein the mass percentage of the active component and the carrier are respectively 0.1-5% and 95-99.9%;

the dehydrofluorination catalyst is any one metal fluoride of Cr, Fe, Co, Ni, Zn, Mg, Ca, Ba, Sr, Al, Ga or In.

2. The method of claim 1, wherein: the hydrogenation catalyst takes palladium or platinum simple substance as active component and CrF₃、FeF₃、CoF₂、NiF₂、ZnF₂、MgF₂、CaF₂、BaF₂、SrF₂、AlF₃、GaF₃Or InF₃Any one of the carriers, wherein the mass percentage of the active component and the carrier are respectively 1-3% and 97-99%.

3. The method of claim 2, wherein: the hydrogenation catalyst takes palladium or platinum simple substance as active component and CrF₃、FeF₃、ZnF₂、MgF₂、AlF₃Any one of the carriers, wherein the mass percentage of the active component and the carrier are respectively 2 percent and 98 percent.

4. The method of claim 1, wherein: the dehydrofluorination catalyst is any one metal fluoride of Cr, Fe, Co, Zn and Al.

5. The method according to any one of claims 1 to 4, wherein: the reaction conditions of the gas-phase hydrogenation reaction I, II are as follows: the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 50 to 250 ℃, and the mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen is 1: 1 to 15, the contact time is 1 to 100s,

the reaction conditions of the dehydrofluorination reaction I, II are: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 300-550 ℃, and the contact time of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 1-100 s.

6. The method of claim 5, wherein: the reaction conditions of the gas phase addition reaction I, II are: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 100-250 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 5 to 15, and the contact time is 10 to 100 s.

7. The method of claim 6, wherein: the reaction conditions of the gas phase addition reaction I, II are: the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 100 to 200 ℃, and the mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen is 1: 5 to 10, and the contact time is 10 to 60 s.

8. The method according to any one of claims 1 to 4, wherein: the reaction conditions of the dehydrofluorination reaction I, II are: the reaction pressure is 0.1-0.3 MPa, the reaction temperature is 350-550 ℃, and the contact time of the 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propylene is 20-100 s.

9. The method of claim 8, wherein: the reaction conditions of the dehydrofluorination reaction I, II are: the reaction pressure is 0.1-0.3 MPa, the reaction temperature is 400-500 ℃, and the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60-100 s.

10. The method of claim 1, wherein: the preparation method of the hydrogenation catalyst comprises the following steps: dissolving soluble salts of noble metals in water, and adjusting the pH value of the solution to 4-6 by using dilute hydrochloric acid to obtain an impregnation solution, wherein the soluble salts of the noble metals are any one or more of palladium nitrate, palladium acetate, palladium chloride, platinum nitrate, platinum acetate, platinum chloride and chloroplatinic acid; dropwise adding the impregnation liquid to the carrier under the conditions of normal pressure and room temperature, maintaining the impregnation for 1-5 hours after the dropwise adding is finished, and filtering and drying to obtain a catalyst precursor; drying the catalyst precursor for 5-10 hours at 100-200 ℃ under the protection of nitrogen, then heating to 250-350 ℃ for roasting for 5-10 hours, and then activating for 8-20 hours at 200-300 ℃ by using a mixed gas with the molar ratio of nitrogen to hydrogen being 4: 1 to prepare the hydrogenation catalyst.

11. The method of claim 1, wherein: the preparation method of the carrier in the hydrogenation catalyst or the dehydrofluorination catalyst comprises the following steps: (1) dissolving soluble salt of metal in water, then dropwise adding a precipitator to enable metal ions to be completely precipitated, adjusting the pH value to 7.0-9.0, enabling the metal ions to be fully precipitated under the stirring condition, aging for 12-36 hours, filtering formed slurry, drying for 6-24 hours at 100-250 ℃, crushing the solid, and performing compression molding to obtain a precursor; (2) roasting the precursor obtained In the step (1) at 300-500 ℃ for 6-24 hours In a nitrogen atmosphere, and activating the precursor for 6-24 hours at 200-400 ℃ by using a mixed gas consisting of hydrogen fluoride and nitrogen In a molar ratio of 1: 2 to prepare a hydrogenation catalyst carrier or a dehydrofluorination catalyst, wherein the soluble salt of metal is any one or more of chloride, nitrate or acetate of Cr, Fe, Co, Ni, Zn, Mg, Ca, Ba, Sr, Al, Ga or In; the precipitant is one or more of ammonia water, sodium hydroxide, potassium hydroxide, cesium hydroxide and rubidium hydroxide.

Technical Field

The invention relates to a method for continuously preparing 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene in a gas phase, in particular to a method for synthesizing 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene by taking octafluoroisobutylene as a starting material through four-step reactions of gas-phase hydrogenation, gas-phase dehydrofluorination, gas-phase hydrogenation and gas-phase dehydrofluorination.

Background

Currently, the existing synthetic routes for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene mainly include the following seven kinds:

route 1: using hexafluoropropylene and difluoromethane as starting materials

The document "Journal of Fluorine Chemistry 108 (2001) 15-20" and patent EP1175380 report a technical route for the synthesis of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene in a two-step reaction starting from hexafluoropropene and difluoromethane (HFC-32): (1) the first step of reaction: reacting hexafluoropropylene with HFC-32 at 50 ℃ for 8 hours under the action of antimony pentafluoride to obtain 1,1,1,2,3,3, 3-heptafluoro-2- (monofluoromethyl) propane with the yield of 90 percent; (2) the second step of reaction: under the protection of argon, 1,1,1,2,3,3, 3-heptafluoro-2- (monofluoromethyl) propane reacts with zinc powder at 500 ℃ for 2 hours to obtain 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene with the yield of 72 percent. The zinc powder can be replaced by iron powder (hydrogen protection, yield 67%), nickel powder (argon protection, yield 58%), pyrolytic graphite (argon protection, yield 57-67%) and the like. This route has the following problems: the temperature of the second reaction step is too high, a large amount of waste solid metal fluoride is generated, and the yield of the product is low.

Route 2: using 3,3, 3-trifluoro-2 (trifluoromethyl) propionic acid chloromethyl ester as raw material

US4739123 reports the reaction of chloromethyl 3,3, 3-trifluoro-2 (trifluoromethyl) propionate with tributylamine at 65 ℃ for 3 hours to give 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene in 76% yield. Tributylamine can be replaced by triethylamine (yield 72%), pyridine (yield 70%). This route has the following disadvantages: (1) raw materials are difficult to obtain; (2) a large amount of waste ammonium salt is produced.

Route 3: using heptafluoro isobutylene methyl ether as initial material

CN107032950 reports a technical route for the synthesis of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene by a four-step reaction using heptafluoro-isobutenyl methyl ether as starting material: (1) the first step of reaction: the method comprises the following steps: anhydrous methanol is used as a solvent, and the molar ratio is 2: 1, reacting heptafluoro-isobutylene methyl ether with potassium borohydride at 10 ℃ for 2 hours, wherein the conversion rate of the heptafluoro-isobutylene methyl ether is 100 percent, and the selectivity of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propenyl methyl ether is 97.3 percent; the second method comprises the following steps: in water, under the action of tetrabutylammonium bromide, the molar ratio is 1: 1, reacting heptafluoro-isobutylene methyl ether with sodium borohydride at 5 ℃ for 1 hour, wherein the mass of tetrabutylammonium bromide is 0.1 percent of that of the heptafluoro-isobutylene methyl ether, so that the conversion rate of the heptafluoro-isobutylene methyl ether is 97.6 percent, and the selectivity of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propenyl methyl ether is 90.8 percent; (2) the second step of reaction: under the action of 75% sulfuric acid, 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propenyl methyl ether reacts for 4 hours at 75 ℃ to obtain hexafluoroisobutyraldehyde with the yield of 95%. 75% sulfuric acid can be replaced by 98% sulfuric acid, 48% hydrobromic acid; (3) the third step of reaction: reacting hexafluoroisobutyraldehyde with hydrogen in a three-neck flask under the action of a 7% Pd/C catalyst, wherein the weight of the catalyst is 2% of that of hexafluoroisobutyraldehyde, the reaction pressure is 0.3MPa, and the reaction is carried out at 40 ℃ for 2 hours, so that the conversion rate of hexafluoroisobutyraldehyde is 100%, and the selectivity of hexafluoroisobutanol is 96.4%; (4) and a fourth step of reaction: in a solvent of 1, 1-dichloroethane, the molar ratio is 1: 3 with potassium hydroxide at 20 ℃ for 3 hours, the conversion of hexafluoroisobutanol was 100%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 70%. This route has the following problems: (1) a liquid phase process is adopted, a large amount of solvent is used, a large amount of waste liquid and waste solid are generated, and the environment is seriously polluted; (2) the raw materials are difficult to obtain.

Route 4: using pentafluoro isobutene as initial raw material

The document "Journal of the Chemical Society; (1953);" p. 3565,3570 "reports a technical scheme for the synthesis of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene by a three-step reaction starting from pentafluoroisobutylene: (1) the first step of reaction: reacting pentafluoro isobutene with chlorine for 20 minutes under the sunlight to obtain 1, 2-dichloro-1, 1,3,3, 3-pentafluoro-2-methylpropane with the yield of 100%; (2) the second step of reaction: in a reactor with a distillation column, 1, 2-dichloro-1, 1,3,3, 3-pentafluoro-2-methylpropane was slowly added dropwise to potassium hydroxide powder at a temperature of 50 ℃ while the temperature of the upper end of the column was kept below 60 ℃ and the reaction product was distilled off while waiting for reflux of the reaction system and then slowly increasing to 120 ℃. The reaction is carried out for 2 days in the process to obtain 3-chloro-3, 3-difluoro-2-trifluoromethyl-1 propylene, the yield is 28 percent, and the boiling point is 52-55 ℃; (3) the third step of reaction: 3-chloro-3, 3-difluoro-2-trifluoromethyl-1-propene and antimony dichloride trifluoride are reacted firstly at 20 ℃ for 5 hours and then at 50 ℃ for 3 hours to obtain 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene with a yield of 93%. This route has the following problems: (1) raw materials are difficult to obtain; (2) the second reaction step, which uses a large amount of KOH as a dehydrochlorination reagent, produces a large amount of waste solids, and the yield of the intermediate 3-chloro-3, 3-difluoro-2-trifluoromethyl-1-propene is too low, resulting in a too low single-pass yield of the entire route for synthesizing 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene.

Route 5: using hexafluoropropylene and sulfur as starting materials

The documents "Organic Syntheses, Coll. Vol.7, p.251 (1990); Vol.63, p.154 (1985)", "Journal of the Chemical Society, 1964, p.2944-: (1) the first step of reaction: the method comprises the following steps: reacting hexafluoropropylene and sulfur in DMF solvent at 40-45 ℃ under the catalytic action of KF to obtain 2,2,4,4-tetrakis (trifluoromethylthio) -1, 3-dithetane with the yield of 80-85% and the boiling point of 106-; the second method comprises the following steps: reacting hexafluoropropylene with sulfur (nitrogen carrying vaporized sulfur into the fixed bed) in a fixed bed containing activated carbon at 425 ℃ to obtain 2,2,4,4-tetrakis (fluoromethyl) -1, 3-dithetane with a yield of 12.8% and a boiling point of 110 ℃; further, thiohexafluoroacetone was obtained in a yield of 34.47%, and the recovery rate of hexafluoropropylene, which is a raw material, was 39.82%; (2) the second step of reaction: the method comprises the following steps: feeding ketene diluted by 2,2,4,4-tetrakis (trifluoromethylthio) -1, 3-dithetane and helium into a reaction tube at 520 ℃ for reaction, wherein the material molar ratio of the 2,2,4,4-tetrakis (trifluoromethylthio) -1, 3-dithetane, helium and the ketene is 20/3/3, the contact time is 4.2 seconds, and the yield of the 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene is 35%; the second method comprises the following steps: the method adopts a method of connecting two reactors in series, namely: firstly, the molar ratio of materials is 1: 1.53 reacting hexafluoropropylene and sulfur at 380-425 deg.c under the action of active carbon to obtain product, cooling the product to 150 deg.c, separating sulfur and reacting other gaseous matter in the second reaction; acetic anhydride was introduced into the reaction mixture at 500 ℃ to react with the first-reacted product to give 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene, and after 3.8 hours of operation, the total yield of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 48.2% (based on the starting material, hexafluoropropylene). This route has the following problems: (1) the overall yield is too low; (2) gas phase continuous processes have some industrial value, however effective metering of sulfur is a technical challenge and can easily block pipelines, so that the insulation of pipelines and metering instruments is important.

Route 6: 1,1,1,3,3, 3-hexafluoro-2-methyl-2-propanol is used as a raw material

The literature "Tetrahedron; vol.27; (1971);" p.3345;)-3355 "reports the reaction of 1,1,1,3,3, 3-hexafluoro-2-methyl-2-propanol as starting material with sulfur tetrafluoride in a sealable vessel at 90 ℃ to 95 ℃ for 18 hours to give 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene with a yield of 72%. This route has the following problems: (1) the raw materials are difficult to obtain, and the yield is low; (2) SF₄Is a highly toxic substance.

Route 7: using octafluoroisobutylene as initial raw material

The literature "Bulletin of the academic of Sciences of the USSR, Division of Chemical Science (English transition)" (1960); p.1312-: (1) the first step of reaction: in a closed vessel, the 1% Pd/alumina catalyst catalyzed molar ratio was 1: reacting octafluoroisobutylene 1.5 with hydrogen at a temperature of 55-60 ℃ to obtain 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane with a yield of 85%; (2) the second step of reaction: in the presence of potassium hydroxide, 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is subjected to dehydrofluorination reaction at the temperature of 40-50 ℃ for 15-20 minutes to obtain 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene with the yield of 76%; (3) the third step of reaction: in a closed vessel, the 1% Pd/alumina catalyst catalyzed molar ratio was 2: reacting 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene of 3 with hydrogen at room temperature to obtain 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane with a yield of 80%; (4) and a fourth step of reaction: in dibutyl ether solvent, under the action of potassium hydroxide, 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is subjected to dehydrofluorination reaction at the temperature of 40-50 ℃ for 20-25 minutes to obtain 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene with the yield of 70%. This route has the following drawbacks: (1) the second step and the fourth step use a large amount of solvent and a large amount of solid strong base, which can generate a large amount of liquid waste and waste solid and seriously pollute the environment; (2) the hydrogenation reaction of the first step and the third step belongs to a batch process, and the yield of the product is low.

At present, no 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene synthetic route which simultaneously meets the characteristics of easy obtainment of raw materials, high single-pass yield, easy realization of gas-phase continuous production and the like exists in the published documents.

Disclosure of Invention

The technical problem to be solved by the invention is to overcome the defects in the background technology and provide a preparation method which has the advantages of easily available raw materials, high single-pass yield, high catalyst activity and easy realization of gas-phase continuous large-scale production of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene.

In order to realize the purpose of the invention, octafluoroisobutylene is used as a starting material, and the 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene is synthesized through four-step reaction of gas-phase hydrogenation, gas-phase dehydrofluorination, gas-phase hydrogenation and gas-phase dehydrofluorination. The reaction equation is as follows:

a process for the continuous preparation of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene in the gas phase, comprising the steps of:

(1) gas-phase hydrogenation reaction I: in the presence of a hydrogenation catalyst, carrying out gas phase addition on octafluoroisobutylene and hydrogen to obtain 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane;

(2) dehydrofluorination reaction I: in the presence of a dehydrofluorination catalyst, 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is used as a raw material to carry out dehydrofluorination reaction to obtain 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propylene;

(3) gas-phase hydrogenation reaction II: in the presence of a hydrogenation catalyst, carrying out gas phase addition on 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propylene and hydrogen to obtain 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane;

(4) dehydrofluorination reaction II: in the presence of a dehydrofluorination catalyst, 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is used as a raw material to carry out dehydrofluorination reaction to obtain 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene;

the hydrogenation catalyst consists of any one of palladium and platinum simple substance and CrF₃、FeF₃、CoF₂、NiF₂、ZnF₂、MgF₂、CaF₂、BaF₂、SrF₂、AlF₃、GaF₃Or InF₃Any one of the carriers, wherein the mass percentage of the active component and the carrier are respectively 0.1-5% and 95-99.9%;

the dehydrofluorination catalyst is any one metal fluoride of Cr, Fe, Co, Ni, Zn, Mg, Ca, Ba, Sr, Al, Ga or In.

The hydrogenation catalyst takes palladium or platinum simple substance as active component and CrF₃、FeF₃、CoF₂、NiF₂、ZnF₂、MgF₂、CaF₂、BaF₂、SrF₂、AlF₃、GaF₃Or InF₃Any one of the carriers, wherein the mass percentage of the active component and the carrier are respectively 1-3% and 97-99%.

The hydrogenation catalyst takes palladium or platinum simple substance as active component and CrF₃、FeF₃、ZnF₂、MgF₂、AlF₃Any one of the carriers, wherein the mass percentage of the active component and the carrier are respectively 2 percent and 98 percent.

The dehydrofluorination catalyst is any one metal fluoride of Cr, Fe, Co, Zn and Al.

The reaction conditions of the gas-phase hydrogenation reaction I, II are as follows: the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 50 to 250 ℃, and the mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen is 1: 1 to 15, the contact time is 1 to 100s,

the reaction conditions of the dehydrofluorination reaction I, II are: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 300-550 ℃, and the contact time of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 1-100 s.

The reaction conditions of the gas phase addition reaction I, II are: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 100-250 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 5 to 15, and the contact time is 10 to 100 s.

The reaction conditions of the gas phase addition reaction I, II are: the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 100 to 200 ℃, and the mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen is 1: 5 to 10, and the contact time is 10 to 60 s.

The reaction conditions of the dehydrofluorination reaction I, II are: the reaction pressure is 0.1-0.3 MPa, the reaction temperature is 350-550 ℃, and the contact time of the 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propylene is 20-100 s.

The reaction conditions of the dehydrofluorination reaction I, II are: the reaction pressure is 0.1-0.3 MPa, the reaction temperature is 400-500 ℃, and the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60-100 s.

The preparation method of the hydrogenation catalyst comprises the following steps: dissolving soluble salts of noble metals in water, and adjusting the pH value of the solution to 4-6 by using dilute hydrochloric acid to obtain an impregnation solution, wherein the soluble salts of the noble metals are any one or more of palladium nitrate, palladium acetate, palladium chloride, platinum nitrate, platinum acetate, platinum chloride and chloroplatinic acid; dropwise adding the impregnation liquid to the carrier under the conditions of normal pressure and room temperature, maintaining the impregnation for 1-5 hours after the dropwise adding is finished, and filtering and drying to obtain a catalyst precursor; drying the catalyst precursor for 5-10 hours at 100-200 ℃ under the protection of nitrogen, then heating to 250-350 ℃ for roasting for 5-10 hours, and then activating for 8-20 hours at 200-300 ℃ by using a mixed gas with the molar ratio of nitrogen to hydrogen being 4: 1 to prepare the hydrogenation catalyst.

The preparation method of the hydrogenation catalyst carrier or the dehydrofluorination catalyst comprises the following steps: (1) dissolving soluble salt of metal in water, then dropwise adding a precipitator to enable metal ions to be completely precipitated, adjusting the pH value to 7.0-9.0, enabling the metal ions to be fully precipitated under the stirring condition, aging for 12-36 hours, filtering formed slurry, drying for 6-24 hours at 100-250 ℃, crushing the solid, and performing compression molding to obtain a precursor; (2) roasting the precursor obtained in the step (1) for 6-24 hours at 300-500 ℃ in a nitrogen atmosphere, and activating for 6-24 hours at 200-400 ℃ by using a mixed gas consisting of hydrogen fluoride and nitrogen in a molar ratio of 1: 2 to prepare a hydrogenation catalyst carrier or a dehydrofluorination catalyst.

The soluble salt of the metal is any one or more of chloride, nitrate or acetate of Cr, Fe, Co, Ni, Zn, Mg, Ca, Ba, Sr, Al, Ga or In; the precipitant is ammonia water.

The precipitator of the invention can be at least one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide and rubidium hydroxide besides ammonia water.

The preparation method of the invention belongs to a gas phase independent circulation continuous process method. Because the boiling point difference between the raw material and the reaction product is large, the raw material and the product can be effectively separated by adopting a distillation mode of a distillation tower, unreacted raw material (comprising octafluoroisobutylene and hydrogen) and unreacted intermediate 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane, 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propylene or 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane are continuously recycled to a reactor to continuously participate in the reaction, and the product 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene and byproduct hydrogen fluoride are extracted out of the system. Wherein the boiling point of the octafluoroisobutylene is 7 ℃ (760 mmHg); the boiling point of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 33-34 ℃ (760 mmHg); the boiling point of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene is 17-18 ℃ (760 mmHg); the boiling point of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 39-40 ℃ (760 mmHg); the boiling point of 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene is 14.5 ℃ (760 mmHg); the boiling point of hydrogen fluoride is 19.5 ℃ (760 mmHg); the boiling point of hydrogen is-258.8 ℃ (760mmHg), and so on.

The type of reactor used for the reaction of the present invention is not critical, and a tubular reactor or the like may be used. Alternatively, adiabatic reactors or isothermal reactors may be used.

The invention has the advantages that:

(1) the method adopts octafluoroisobutylene as a starting material to synthesize the 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene, and has high one-way yield;

(2) the hydrogenation catalyst and the dehydrofluorination catalyst in the invention have the characteristics of high activity and long service life;

(3) the invention adopts a gas phase method to prepare 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene, and the materials which are not completely reacted are independently circulated through a gas phase independent circulation process, so that the initial raw materials can be almost completely converted into the 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene, and finally the product 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene is extracted from a process system, thereby not generating liquid waste and waste gas and realizing green production.

Drawings

The invention is described in further detail below with reference to the accompanying drawings.

FIG. 1 shows a flow chart of a preparation process for preparing 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene by using octafluoroisobutylene as a starting material through four steps of a gas-phase hydrogenation reaction, a dehydrofluorination reaction, a gas-phase hydrogenation reaction and a dehydrofluorination reaction.

The reference numerals in fig. 1 have the following meanings. Pipeline: 1. 2,3, 5, 7, 8, 10, 11, 13, 14, 16, 17, 19, 20, 21, 22, 24, 26, 27, 29, 30, 32, 33, 35, 36, 38, and 39; a first reactor: 4; a second reactor: 9; a third reactor: 23; a fourth reactor: 28; a first distillation column: 6; first HF adsorption column: 12; first HF stripper: 15; a second distillation column: 18; a third distillation column: 25; second HF adsorption column: 31; second HF resolution column: 34; a fourth distillation column: 37.

Detailed Description

The present invention is described in further detail with reference to fig. 1. But not to limit the invention. Fresh octafluoroisobutylene enters a first reactor 4 filled with a hydrogenation catalyst through a pipeline 3 together with fresh hydrogen through a pipeline 2 and a mixture of octafluoroisobutylene and hydrogen recycled through a pipeline 7 for gas-phase hydrogenation reaction, the reaction product flow is 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane and unreacted octafluoroisobutylene and hydrogen, and the reaction product flows through a pipeline 5 and enters a first distillation tower 6 for separation; the tower top component of the first distillation tower 6 is octafluoroisobutylene and hydrogen, the tower bottom component is 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane, and the tower top component continuously circulates to the first reactor 4 through pipelines 7 and 3 to continue to react; the bottom components of the first distillation tower 6 enter a second reactor 9 filled with a dehydrofluorination catalyst through a pipeline 11 together with 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane recycled through a pipeline 20 through a pipeline 8 to carry out gas phase dehydrofluorination reaction, the reaction product flow is 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene, hydrogen fluoride and unreacted 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane, and the reaction product flows through a pipeline 10 to enter a first HF adsorption tower 12 filled with sulfuric acid with the mass percentage concentration of 98-100% for adsorption; the top components of the first HF adsorption column 12 are 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene and 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane, and they are separated by feeding them to the second distillation column 18 through the line 13; tower kettle components of the first HF adsorption tower 12 enter a first HF desorption tower 15 through a pipeline 14 for desorption; the tower kettle component of the first HF analysis tower 15 is sulfuric acid, the tower top component is HF, the tower kettle component circulates to the HF adsorption tower for continuous use through a pipeline 17, and the tower top component is subjected to subsequent drying and rectification to obtain high-purity hydrogen fluoride or is prepared into hydrofluoric acid with various concentrations for sale; the bottom component of the second distillation column 18 is 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane, the top component is 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene, the bottom component is recycled to the second reaction 9 through a pipeline 20 and a pipeline 11 for further reaction, and the top component is recycled to a third reactor 23 filled with a hydrogenation catalyst through a pipeline 22 for gas-phase hydrogenation reaction together with fresh hydrogen through a pipeline 21 and a mixture of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene and hydrogen recycled through a pipeline 26, wherein the reaction product flow is 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane and unreacted 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene and hydrogen, and the reaction product flows through a pipeline 24 and enters a third distillation tower 25 for separation; the tower top component of the third distillation tower 25 is 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propylene and hydrogen, the tower bottom component is 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane, and the tower top component continuously circulates to the third reactor 23 through pipelines 26 and 22 to continue to react; the bottom components of the third distillation tower 25 enter a fourth reactor 28 filled with a dehydrofluorination catalyst through a pipeline 29 together with 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane recycled through a pipeline 39 through a pipeline 27 to undergo a gas phase dehydrofluorination reaction, the reaction product streams are 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene, hydrogen fluoride and unreacted 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane, and the reaction product flows through a pipeline 30 to enter a second HF adsorption tower 31 filled with sulfuric acid with a mass percentage concentration of 98% to 100% for adsorption; the overhead components of the second HF adsorption column 31, which are 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene and 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane, are fed to a fourth distillation column 37 via a line 32 for separation; tower kettle components of the second HF adsorption tower 31 enter a second HF desorption tower 34 through a pipeline 33 for desorption; the tower kettle component of the second HF analysis tower 34 is sulfuric acid, the tower top component is HF, the tower kettle component circulates to the second HF adsorption tower 31 through a pipeline 36 for continuous use, and the tower top component is subjected to subsequent drying and rectification to obtain high-purity hydrogen fluoride or is prepared into hydrofluoric acid with various concentrations for sale; the bottom component of the fourth distillation column 37 is 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane, the top component is 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene, the bottom component is circulated to the fourth reaction 28 through a pipeline 39 and a pipeline 29 for continuous reaction, and the top component is subjected to subsequent deacidification, dehydration and rectification to obtain the target product 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene.

An analytical instrument: shimadzu GC-2010, column model InterCap1 (i.d.0.25 mm; length 60 m; J & W Scientific Inc.).

Gas chromatographic analysis method: high purity helium and hydrogen fluoride are used as carrier gases. The temperature of the detector is 240 ℃, the temperature of the vaporization chamber is 150 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 10 minutes, the temperature is raised to 240 ℃ at the rate of 20 ℃/min, and the temperature is kept for 10 minutes.

Preparing a catalyst:

1. preparation of hydrogenation catalyst:

(1) preparation of the carrier of the hydrogenation catalyst: dissolving aluminum trichloride in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.5, then aging for 24 hours, washing with water, filtering, drying in an oven at 120 ℃ for 15 hours, crushing the obtained solid, tabletting and molding to obtain a precursor of the carrier, filling 10mL of the precursor of the carrier into a tubular reactor made of Monel material with the inner diameter of 1/2 inches and the length of 30cm, introducing nitrogen, roasting at 350 ℃ for 12 hours, wherein the space velocity of the nitrogen is 200 hours^-1Then, the temperature is reduced to 300 ℃, and simultaneously the mass ratio of the introduced substances is 1: 2 hydrogen fluoride and nitrogen gas mixture, total gas space velocityIs 220h^-1And activating for 12 hours, and stopping the mixed gas to prepare the aluminum fluoride.

Other supports may be prepared instead of other soluble metal salts.

(2) Preparation of hydrogenation catalyst by impregnation: according to Pd, AlF₃The mass percentage of the two is respectively 2%: dissolving 98% palladium chloride in water, and adjusting the pH value of the solution to 4-6 by using dilute hydrochloric acid to obtain a steeping liquor; dropwise adding the impregnation liquid to the carrier under the conditions of normal pressure and room temperature, maintaining impregnation for 4 hours after dropwise adding, filtering and drying to obtain a catalyst precursor; drying the catalyst precursor for 8 hours at 120 ℃ under the protection of nitrogen, then heating to 300 ℃ for roasting for 8 hours, and then activating for 14 hours at 250 ℃ by using mixed gas with the molar ratio of nitrogen to hydrogen being 4: 1 to prepare the hydrogenation catalyst.

Other hydrogenation catalysts can be prepared by replacing the types and the contents of the active metals and the carriers.

2. Preparation of dehydrofluorination catalyst: dissolving chromium trichloride in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.5, then aging for 24 hours, washing with water, filtering, drying in an oven at 120 ℃ for 15 hours, crushing the obtained solid, tabletting and forming to obtain a catalyst precursor, filling 10mL of the catalyst precursor into a tubular reactor made of Monel material with the inner diameter of 1/2 inches and the length of 30cm, introducing nitrogen, roasting at 350 ℃ for 12 hours, wherein the space velocity of the nitrogen is 200 hours^-1Then, the temperature is reduced to 300 ℃, and simultaneously the mass ratio of the introduced substances is 1: 2, the total space velocity of the gas is 220h^-1And activating for 12 hours, and stopping the mixed gas to prepare the chromium fluoride.

Other dehydrofluorination catalysts can be prepared by replacing other soluble metal salts.

The catalysts in the following examples were prepared as described above, and the catalysts in the comparative examples were all commercially available products.

Example 1

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: inverse directionThe temperature should be 50 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 73.4%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.8%.

Example 2

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 100 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 93.8%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.6%.

Example 3

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 100%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.5%.

Example 4

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 200 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 100%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.1%.

Example 5

At inner diameter 1/2A tubular reactor made of Incan alloy with the length of 30cm and the length of 2 percent of Pd/98 percent of AlF is filled in the tubular reactor₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 250 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 100%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 98.2%.

Example 6

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 1, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 59.7%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.6%.

Example 7

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 5, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 91.7%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.5%.

Example 8

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 15, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 100%, and 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl)) The selectivity to propane was 99.4%.

Example 9

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 1s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 48.5%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.8%.

Example 10

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 10s and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 89.3%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.7%.

Example 11

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 100s and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 100%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 97.5%.

Example 12

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% CrF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10 hours of operation, the reaction product is washed by water, washed by alkali and dried,the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 96.4%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.2%.

Example 13

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was packed with 2% Pd/98% FeF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 95.4%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 99.0%.

Example 14

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% MgF₂10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 100%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 98.6%.

Example 15

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was packed with 2% Pd/98% ZnF₂10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 91.6%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 98.7%.

Example 16

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 300 ℃, and the reaction temperature is 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propaneThe contact time of (3) was 60s and the reaction pressure was 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 75.4%, and the selectivity for 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 99.7%.

Example 17

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 350 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 82.5%, and the selectivity for 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 99.5%.

Example 18

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 100%, and the selectivity of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 99.3%.

Example 19

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 450 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 100%, and the selectivity of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 99.1%.

Example 20

Inconel alloy with inner diameter of 1/2 inches and length of 30cmCrF is filled in the tubular reactor₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 500 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 100%, and the selectivity for 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 97.9%.

Example 21

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst was prepared. The reaction conditions are as follows: the reaction temperature is 550 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 100%, and the selectivity for 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 97.0%.

Example 22

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 1s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 53.7%, and the selectivity for 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 99.5%.

Example 23

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 20s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 74.6%, 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propaneThe selectivity to alkene was 99.2%.

Example 24

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 100s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 100%, and the selectivity for 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 98.8%.

Example 25

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.3 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 88.1%, and the selectivity of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 99.4%.

Example 26

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.5 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 59.4%, and the selectivity of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 98.5%.

Example 27

FeF was charged into a tubular reactor of an Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After running for 10h, the reaction product is washed by water, washed by alkali and dried, and the gas phase is takenThe organic phase was subjected to GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 91.7%, and the selectivity for 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 99.0%.

Example 28

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was packed with AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 100%, and the selectivity for 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 97.3%.

Example 29

CoF was charged into a tubular reactor of an Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₂10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 90.2%, and the selectivity of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 99.1%.

Example 30

ZnF was charged into a tubular reactor of an Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₂10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 87.2%, and the selectivity of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 99.5%.

Example 31

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 50 ℃,1,3The mass ratio of 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen was 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 67.1%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.9%.

Example 32

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 100 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 92.4%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.7%.

Example 33

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 100%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.4%.

Example 34

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 200 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propaneThe conversion of alkene was 100% and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 97.3%.

Example 35

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 250 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 100%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 94.7%.

Example 36

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 1, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 61.4%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.6%.

Example 37

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 5, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 87.4%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.4%.

Example 38

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃CatalysisDose 10 mL. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 15, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 100%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.4%.

Example 39

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 1s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 50.3%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.7%.

Example 40

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 10s and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 84.5%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.6%.

EXAMPLE 41

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% AlF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 100s and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis.The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 100%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 96.2%.

Example 42

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% CrF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 100%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.1%.

Example 43

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was packed with 2% Pd/98% FeF₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 98.4%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.0%.

Example 44

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 2% Pd/98% MgF₂10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 100%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.2%.

Example 45

Made of inconel having an inner diameter of 1/2 inches and a length of 30cmThe tubular reactor is filled with 2% Pd/98% ZnF₂10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 98.1%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 99.2%.

Example 46

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 300 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 65.8%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.7%.

Example 47

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 350 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 82.4%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.6%.

Example 48

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 10The selectivity to 0%, 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.6%.

Example 49

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 450 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 100%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.3%.

Example 50

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 500 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 100%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 98.2%.

Example 51

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 550 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 100%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 94.3%.

Example 52

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 1s, and the reaction pressure is 0.1 MPa. After running for 10h, the reactionThe product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 65.3%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.5%.

Example 53

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 20s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 87.6%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.4%.

Example 54

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 100s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 100%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.2%.

Example 55

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.3 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 81.4%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.1%.

Example 56

CrF was charged into a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃Catalyst 10mL. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.5 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 53.7%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 98.1%.

Example 57

FeF was charged into a tubular reactor of an Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 97.5%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.5%.

Example 58

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was packed with AlF₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 100%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 95.4%.

Example 59

CoF was charged into a tubular reactor of an Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₂10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 94.7%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.2%.

Example 60

ZnF was charged into a tubular reactor of an Incan alloy having an inner diameter of 1/2 inches and a length of 30cm₂10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 91.9%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 99.4%.

Comparative example 1

A tubular reactor made of a Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with commercially available 2% Pd/98% Al₂O₃10mL of catalyst. The reaction conditions are as follows: the reaction temperature is 150 ℃, and the mass ratio of octafluoroisobutylene to hydrogen is 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of octafluoroisobutylene was 53.4%, and the selectivity of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 87.2%.

Comparative example 2

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with commercially available CrF₃10mL of the catalyst was used. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (difluoromethyl) propane was 46.8%, and the selectivity for 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 91.6%.

Comparative example 3

A tubular reactor made of a Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with commercially available 2% Pd/98% Al₂O₃10mL of catalyst. The reaction conditions are as follows: reaction temperature 150 ℃, and mass ratio of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene to hydrogen gas of 1: 10, the contact time is 60s, and the reaction pressure is 0.1 MPa. After the operation is carried out for 10 hours,the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene was 42.1%, and the selectivity for 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 83.7%.

Comparative example 4

A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with commercially available CrF₃10mL of the catalyst was used. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane is 60s, and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3,3, 3-hexafluoro-2- (monofluoromethyl) propane was 38.4%, and the selectivity for 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propene was 92.7%.