CN104841413B - Aluminum-based catalyst for preparing vinyl fluoride from 1, 1-difluoroethane, and preparation method and application thereof - Google Patents
Aluminum-based catalyst for preparing vinyl fluoride from 1, 1-difluoroethane, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an aluminum-based catalyst for preparing vinyl fluoride by gas phase dehydrofluorination of 1, 1-difluoroethane, which comprises a main active component aluminum and a modification component, wherein the modification component is one, two or more than three of lanthanum, yttrium, cerium, zirconium, zinc, magnesium, nickel, cobalt, iron, manganese, tin and bismuth. The aluminum-based catalyst disclosed by the invention can obviously reduce the reaction temperature for preparing vinyl fluoride by gas-phase dehydrofluorination of 1, 1-difluoroethane and improve the conversion rate and selectivity.
Description
Technical Field
The invention relates to an aluminum-based catalyst, in particular to an aluminum-based catalyst for preparing vinyl fluoride from 1, 1-difluoroethane and a preparation method thereof.
Background
Vinyl Fluoride (VF) is an important fluorine-containing monomer, and is mainly used for preparing polyvinyl fluoride (PVF). PVF is a fluororesin having the lowest fluorine content and the lowest density, has excellent chemical corrosion resistance, hydrophobicity, abrasion resistance, aging resistance, non-adhesiveness and the like, and has been widely used for protective layers of building materials, packaging of aviation industry and solar cells, inner wall coatings of packaging containers, corrosion prevention of oil field oil pipelines and the like.
The prior art discloses preparation routes of various VF monomers, wherein the production process technology taking acetylene and HF as raw materials is mature, but the problems of short service life of a catalyst, low VF selectivity, large three-waste amount, flammability and explosiveness of the raw material acetylene and the like exist. VF is prepared by gas phase dehydrofluorination of 1, 1-difluoroethane (HFC-152 a), thereby avoiding the use of inflammable and explosive acetylene, having the advantages of simple preparation process, high VF selectivity, less impurities and the like, being beneficial to improving the VF quality and further improving the quality of a PVF film.
U.S. Pat. No. 2,9799631 reports that HFC-152a is pyrolyzed at 562-797 ℃ to VF without a catalyst, and the reaction conversion rate is only 40%. Under the action of a catalyst, e.g. CaF2Is a catalyst, and the conversion rate is 66 percent at 500 ℃; the conversion rate can be increased to 78% at 600 ℃ by using activated carbon as a catalyst. The method has high reaction temperature and low HFC-152a conversion rate.
U.S. Pat. No. 5,5880315 reports a process for the preparation of VF by thermal cracking of HFC-152a, using MAlF5(H2O)2Or NH4MAlF6(H2O) (M = Zn, Mg) is a catalyst comprising MgF2/AlF3、ZnF2/AlF3、MgF2-ZnF2/AlF3Wherein the molar ratio of Mg to Al, Zn to Al and Mg + Zn to Al is 1: 1. At 300 ℃ and space velocity of 600h-1Reacting for 1h and 48h under the condition, ZnF2/β-AlF3The conversion rate of the catalyst to HFC-152a is only 44.8 percent and 43.5 percent, and MgF2/β-AlF3The catalyst conversion to HFC-152a was only 42.8% and 43.4%. The method has low HFC-152a conversion rate.
US patent US6262321B1 reports on MgF2/AlF3、ZnF2/AlF3、MgF2-ZnF2/AlF3A method for preparing VF from HFC-152a under the action of a series of catalysts (wherein the molar ratio of Mg to Al, Zn to Al and Mg + Zn to Al is more than or equal to 4 to 1). As a specific embodiment, MgF2/AlF3(Mg: Al = 9: 1) at 275 ℃ and a space velocity of 514h-1The reaction under the condition can reach 99.9 percent of VF selectivity, but the conversion rate of HFC-152a is only 40 percent. The method has low conversion rate of HFC-152a when reacting at lower temperature, resulting in low space-time yield and production efficiency of the catalyst.
Chinese patent CN103071516A reports on Ni-Co-Ag-TbF3/AlF3-Al2O3Method for preparing VF (nickel, cobalt, silver, Tb =1:1:1: 1) from HFC-152a under the action of catalyst at 420 ℃ and space velocity of 700h-1Under the conditions of (1), the reaction conversion was 82.5% and the VF selectivity was 99.3%. Meanwhile, the Ni/Co content ratio, the reaction temperature, the addition of Tb and Ag, the Ni/Co/Ag/Tb content ratio have larger influence on the catalyst, and the reaction temperature is the optimal temperature at 420 ℃. The preparation method of the catalyst is complex and is not beneficial to industrial scale-up.
Disclosure of Invention
The inventor discovers that during the process of preparing VF by dehydrofluorination of 1, 1-difluoroethane: when aluminum is used as a main component, one, two or more than three components selected from lanthanum, yttrium, cerium, zirconium, zinc, magnesium, nickel, cobalt, iron, manganese, tin and bismuth are used as modified metal components, and the molar ratio of the aluminum to the modified metal components is reasonably controlled, so that the VF selectivity and the HFC-152a conversion rate can be effectively improved, and the reaction temperature can be remarkably reduced. The prior art does not give any technical teaching to this.
The technical scheme adopted by the invention is as follows:
an aluminum-based catalyst is used for preparing vinyl fluoride by gas phase dehydrofluorination of 1, 1-difluoroethane, and comprises a main active component aluminum and a modification component, wherein the modification component is one, two or more of lanthanum, yttrium, cerium, zirconium, zinc, magnesium, nickel, cobalt, iron, manganese, tin and bismuth, and the molar ratio of aluminum to the modification component is 1: 0.01-0.3;
when the modifying component is zinc and/or magnesium, the molar ratio of the aluminum to the modifying component is 1: 0.03-0.27.
Preferably, in the catalyst, the molar ratio of the aluminum to the modifying component is 1:0.04 to 0.25; the modified component is preferably selected from one, two or more than three of lanthanum, yttrium, zirconium, zinc, nickel, cobalt and iron.
The invention also provides a preparation method of the aluminum-based catalyst. When prepared according to the dipping method, comprises the following steps:
(1) weighing a certain amount of aluminum-containing compound, adding the aluminum-containing compound into soluble salt of the modified component, standing for 6-12 h, drying at 105-150 ℃ for 10-24 h,
controlling the molar ratio of the aluminum to the modification component to be 1: 0.01-0.3, and when the modification component is zinc and/or magnesium, controlling the molar ratio of the aluminum to the modification component to be 1: 0.03-0.27;
(2) roasting the substance prepared in the step (1) at the temperature of 300-800 ℃ for 2-6 h to obtain an aluminum-based catalyst precursor;
(3) and (3) tabletting and forming the precursor of the aluminum-based catalyst prepared in the step (2), then drying the precursor for 2-12 h at the temperature of 200-400 ℃ by using inert gas, and finally carrying out fluorination treatment for 10-24 h at the temperature of 150-400 ℃ to obtain the aluminum-based catalyst.
The aluminium-containing compound used above is preferably selected from aluminium oxide, halogenated aluminium oxide or oxyhalogen oxide, and the soluble salt of the modifying component is preferably selected from soluble nitrate, soluble sulphate or soluble chloride of the modifying component.
When the aluminum-based catalyst is prepared according to a blending method, the following steps are included:
(1) weighing a certain amount of an aluminum-containing compound, a modified component metal simple substance, a modified component oxide or a modified component hydroxide, and performing ball milling and blending to obtain a blend, wherein the molar ratio of aluminum to the modified component is controlled to be 1: 0.01-0.3, and when the modified component is zinc and/or magnesium, the molar ratio of aluminum to the modified component is 1: 0.03-0.27;
(2) carrying out wet mixing extrusion forming on the blend prepared in the step (1), and roasting at the temperature of 300-800 ℃ for 2-6 h to obtain an aluminum-based catalyst precursor;
(3) and (3) drying the precursor of the aluminum-based catalyst prepared in the step (2) by using inert gas at the temperature of 200-400 ℃ for 2-12 h, and then carrying out fluorination treatment at the temperature of 150-400 ℃ for 10-24 h to obtain the aluminum-based catalyst.
The aluminum-containing compound used above is preferably selected from the group consisting of aluminum oxide, aluminum hydroxide, halogenated aluminum oxide, hydrated halogenated aluminum oxide and aluminum oxyhalide.
When the aluminum-based catalyst is prepared by the dipping method or the blending method, the fluorination treatment in the step (3) is preferably performed by introducing a mixed gas composed of HF and an inert gas according to a molar ratio of 1: 4-10, and gradually increasing the concentration of HF in the mixed gas until the mixed gas is finally introduced to be pure hydrogen fluoride.
When the aluminum-based catalyst is used for preparing vinyl fluoride by gas phase dehydrofluorination of 1, 1-difluoroethane, the reaction temperature is preferably 250-400 ℃, and more preferably 300-350 ℃; the space velocity is preferably 100-2000 h-1More preferably 100 to 1000 hours-1。
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
Weighing 20.39g of gamma-Al according to the molar ratio of the Al to the Y of 1: 0.052O3And 7.66g of Y (NO)3)3·6H2O, first, Y (NO)3)3·6H2Dissolving O in water, adding gamma-Al2O3Standing for 10h for full impregnation, drying at 105 deg.C for 24h, and calcining at 600 deg.C for 3h to obtain catalyst precursor Y2O3/γ-Al2O3. Drying the catalyst precursor in situ with nitrogen at 200 deg.C for 6h, and introducing HF: N2Fluorinating for 4h at 180 ℃ in a mixed gas of 1: 10, then heating to 340 ℃ at the speed of 1 ℃/min, gradually increasing the concentration of hydrogen fluoride until pure hydrogen fluoride is introduced for fluorination for 8h at the later stage, and obtaining the aluminum-based catalyst.
The prepared aluminum-based catalyst is used for the gas phase dehydrofluorination reaction of 1, 1-difluoroethane, the reaction temperature is controlled to be 250-400 ℃, and the space velocity is controlled to be 100-1000 h-1The conversion of HFC-152a and the selectivity of VF are shown in Table 1.
TABLE 1
| Reaction temperature (. degree.C.) | Space velocity (h)-1) | Conversion (%) | VF selectivity (%) |
| 350 | 100 | 79.5 | 97.1 |
| 350 | 200 | 76.3 | 98.0 |
| 350 | 300 | 74.2 | 98.2 |
| 350 | 400 | 70.3 | 98.5 |
| 350 | 500 | 68.4 | 98.8 |
| 350 | 600 | 61.8 | 99.1 |
| 350 | 1000 | 50.2 | 99.5 |
| 250 | 300 | 43.1 | 99.4 |
| 300 | 300 | 50.7 | 98.9 |
| 400 | 300 | 81.1 | 97.8 |
Example 2
Weighing 20.39g of gamma-Al according to the molar ratio of Al, Y and Ni of 1: 0.04: 0.012O36.13g of Y (NO)3)3·6H2O, 1.16g of Ni (NO)3)2·6H2O, first, Y (NO)3)3·6H2O、Ni(NO3)2·6H2Dissolving O in water to dissolve themThen adding gamma-Al2O3Standing for 12h to fully soak the catalyst, drying at 110 ℃ for 12h, and finally roasting at 800 ℃ for 2h to obtain a catalyst precursor NiO-Y2O3/γ-Al2O3. The catalyst precursor is dried in situ for 4h at the temperature of 300 ℃ by using nitrogen, and then HF: N is introduced2Fluorinating for 4h at 180 ℃ in a mixed gas of 1: 10, then heating to 340 ℃ at the speed of 1 ℃/min, gradually increasing the concentration of hydrogen fluoride until pure hydrogen fluoride is introduced for fluorination for 8h at the later stage, and obtaining the aluminum-based catalyst.
The prepared aluminum-based catalyst is used for the gas phase dehydrofluorination reaction of 1, 1-difluoroethane, the reaction temperature is controlled to be 350 ℃, and the space velocity is controlled to be 300h-1The conversion of HFC-152a and the selectivity to VF are shown in Table 2.
TABLE 2
| Reaction time (h) | Conversion (%) | VF selectivity (%) |
| 1 | 79.8 | 99.1 |
| 12 | 74.4 | 99.5 |
| 48 | 75.6 | 99.2 |
Example 3
Weighing 20.39g of gamma-Al according to the molar ratio of Al, Y, Ni and Co of 1: 0.03: 0.012O34.60g of Y (NO)3)3·6H2O, 1.16g of Ni (NO)3)2·6H2O, 1.43g of Co (NO)3)2·6H2O, first, Y (NO)3)3·6H2O、Ni(NO3)2·6H2O、Co(NO3)2·6H2Dissolving O in water, dissolving the three, and adding gamma-Al2O3Standing for 6h to fully soak the catalyst, drying at 150 ℃ for 10h, and finally roasting at 500 ℃ for 6h to obtain a catalyst precursor Co3O4-NiO-Y2O3/γ-Al2O3. Drying the catalyst precursor in situ with nitrogen at 400 deg.C for 2h, and introducing HF: N2Fluorinating for 4h at 180 ℃ in a mixed gas of 1: 10, then heating to 340 ℃ at the speed of 1 ℃/min, gradually increasing the concentration of hydrogen fluoride until pure hydrogen fluoride is introduced for fluorination for 8h at the later stage, and obtaining the aluminum-based catalyst.
The prepared aluminum-based catalyst is used for the gas phase dehydrofluorination reaction of 1, 1-difluoroethane, the reaction temperature is controlled to be 400 ℃, and the space velocity is controlled to be 300h-1The conversion of HFC-152a and the selectivity to VF are shown in Table 3.
TABLE 3
| Reaction time (h) | Conversion (%) | VF selectivity (%) |
| 1 | 83.2 | 97.9 |
| 12 | 81.7 | 98.0 |
| 48 | 82.1 | 97.8 |
Example 4
78.00g of Al (OH) were weighed out in a molar ratio of Al to Fe of 1: 0.13And 10.69g of Fe (OH)3Ball milling and blending, then extruding and forming the uniformly mixed powder by a wet mixing extrusion method, and roasting at the temperature of 500 ℃ for 6 hours to obtain a precursor Fe of the catalyst2O3-Al2O3. Drying the catalyst precursor in situ with nitrogen at 200 deg.C for 6h, and introducing HF: N2Fluorinating for 4h at 180 ℃ in a mixed gas of 1: 10, then heating to 340 ℃ at the speed of 1 ℃/min, gradually increasing the concentration of hydrogen fluoride until pure hydrogen fluoride is introduced for fluorination for 8h at the later stage, and obtaining the aluminum-based catalyst.
The prepared aluminum-based catalyst is used for the gas phase dehydrofluorination reaction of 1, 1-difluoroethane, the reaction temperature is controlled to be 350 ℃, and the space velocity is controlled to be 200h-1The conversion of HFC-152a and the selectivity to VF are shown in Table 4.
TABLE 4
| Reaction time (h) | Conversion (%) | VF selectivity (%) |
| 1 | 78.1 | 98.8 |
| 120 | 77.6 | 98.8 |
| 240 | 74.3 | 98.9 |
| 500 | 60.5 | 98.7 |
Example 5
101.96g of Al were weighed out in a molar ratio of Al to Fe to Ni of 1: 0.08: 0.022O36.39g of Fe2O3And 1.49g of NiO, performing ball milling and blending, then performing extrusion forming on the uniformly mixed powder by a wet mixing extrusion method, and treating at the temperature of 600 ℃ for 3 hours to obtain a precursor NiO-Fe of the catalyst2O3-Al2O3. The catalyst precursor is dried in situ for 2h at the temperature of 300 ℃ by nitrogen, and then HF: N is introduced2Fluorinating for 4h at 180 ℃ in a mixed gas of 1: 10, then heating to 340 ℃ at the speed of 1 ℃/min, gradually increasing the concentration of hydrogen fluoride until pure hydrogen fluoride is introduced for fluorination for 8h at the later stage, and obtaining the aluminum-based catalyst.
The prepared aluminum-based catalyst is used for the gas phase dehydrofluorination reaction of 1, 1-difluoroethane, the reaction temperature is controlled to be 350 ℃, and the space velocity is controlled to be 200h-1The conversion of HFC-152a and the selectivity to VF are shown in Table 5.
TABLE 5
| Reaction time (h) | Conversion (%) | VF selectivity (%) |
| 1 | 75.6 | 99.9 |
| 120 | 73.0 | 99.9 |
| 240 | 73.1 | 99.8 |
| 500 | 59.7 | 99.7 |
Example 6
83.98g of gamma-AlF are weighed according to the molar ratio of Al, Zn and La of 1: 0.15: 0.01312.21g of ZnO, 3.26g of La2O3Ball milling and blending, then extruding and forming the uniformly mixed powder by a wet mixing extrusion method, and roasting at the temperature of 300 ℃ for 3h to obtain a precursor La of the catalyst2O3-ZnO-AlF3. The catalyst precursor is dried in situ for 2h at the temperature of 300 ℃ by nitrogen, and then HF: N is introduced2Fluorinating for 4h at 200 ℃ in a mixed gas of 1:4, then heating to 360 ℃ at the speed of 1 ℃/min, gradually increasing the concentration of hydrogen fluoride until pure hydrogen fluoride is introduced for fluorination for 6h at the later stage, and obtaining the aluminum-based catalyst.
The prepared aluminum-based catalyst is used for the gas phase dehydrofluorination reaction of 1, 1-difluoroethane, the reaction temperature is controlled to be 350 ℃, and the space velocity is controlled to be 500h-1，HFC-152a and VF selectivity are shown in table 6.
TABLE 6
| Reaction time (h) | Conversion (%) | VF selectivity (%) |
| 1 | 66.3 | 99.0 |
| 12 | 66.1 | 99.1 |
| 48 | 66.2 | 98.9 |
| 180 | 66.0 | 98.8 |
Example 7
83.98g of gamma-AlF are weighed according to the molar ratio of Al, Zn, Zr and La of 1: 0.15: 0.05: 0.01312.21g of ZnO, 6.16g of ZrO2And 3.26g of La2O3And the rest of the steps are the same as example 6 to obtain the aluminum-based catalyst.
The prepared aluminum-based catalyst is used for the gas phase dehydrofluorination reaction of 1, 1-difluoroethane, the reaction temperature is controlled to be 350 ℃, and the space velocity is controlled to be 500h-1The conversion of HFC-152a and the selectivity to VF are shown in Table 7.
TABLE 7
| Reaction time (h) | Conversion (%) | VF selectivity (%) |
| 1 | 67.8 | 99.9 |
| 12 | 67.6 | 99.9 |
| 48 | 67.9 | 99.8 |
| 180 | 67.5 | 99.7 |
Comparative example 1
Subjecting AlF to3Extrusion molding is carried out by a wet mixing extrusion method, and roasting treatment is carried out for 3h at the temperature of 300 ℃ to obtain the catalyst precursor. The catalyst precursor is dried in situ for 2h at the temperature of 300 ℃ by nitrogen, and then HF: N is introduced2Fluorinating for 4h at 200 ℃ in a mixed gas of 1:4, then heating to 360 ℃ at the speed of 1 ℃/min, gradually increasing the concentration of hydrogen fluoride until pure hydrofluoride is introduced for 6h at the later stage, and obtaining the catalyst.
The prepared catalyst is used for the gas phase dehydrofluorination reaction of 1, 1-difluoroethane,the reaction temperature is controlled to be 250-350 ℃, and the space velocity is controlled to be 500h-1The conversion of HFC-152a and the selectivity to VF are shown in Table 8. Simultaneously considering the stability of the catalyst, controlling the reaction temperature at 350 ℃ and the space velocity at 500h-1The conversion of HFC-152a and the selectivity of VF after 120 hours of reaction are shown in Table 9.
TABLE 8
| Reaction temperature (. degree.C.) | Conversion (%) | VF selectivity (%) |
| 250 | 14.0 | 99.0 |
| 300 | 26.1 | 98.5 |
| 350 | 45.2 | 97.4 |
TABLE 9
| Reaction time (h) | Conversion (%) | VF selectivity (%) |
| 1 | 45.2 | 97.4 |
| 120 | 38.7 | 97.2 |
As can be seen from Table 8, AlF without addition of modifying component3When the reaction temperature of the catalyst is less than or equal to 350 ℃, the conversion rate of HFC-152a is lower, and the activity of the catalyst is poorer. As can be seen from Table 9, AlF without addition of modifying component3The stability of the catalyst is poor.
Therefore, the activity and stability of the catalyst can be obviously improved by modifying the aluminum-based catalyst, so that the reaction for preparing the vinyl fluoride by the gas-phase dehydrofluorination of the 1, 1-difluoroethane can have better activity and stability under the condition of lower temperature.
Claims (8)
1. A method for preparing vinyl fluoride by gas phase dehydrofluorination of 1, 1-difluoroethane is characterized in that:
an aluminum-based catalyst is adopted in the reaction process of preparing vinyl fluoride by gas phase dehydrofluorination of 1, 1-difluoroethane, the reaction temperature is 300-350 ℃, and the space velocity is 100-1000 h-1；
The aluminum-based catalyst contains a main active component aluminum and a modification component, wherein the modification component is one, two or more of lanthanum, yttrium, cerium, zirconium, manganese, tin and bismuth, and the molar ratio of aluminum to the modification component is 1: 0.01-0.3.
2. The process for the vapor phase dehydrofluorination of 1, 1-difluoroethane to produce vinyl fluoride according to claim 1, wherein the molar ratio of aluminum to the modifying component is 1:0.04 to 0.25.
3. The process for the vapor phase dehydrofluorination of 1, 1-difluoroethane to produce vinyl fluoride according to claim 1, wherein said modifying component is selected from the group consisting of one, two or more of lanthanum, yttrium and zirconium.
4. Process for the preparation of vinyl fluoride by gas phase dehydrofluorination of 1, 1-difluoroethane according to claim 1, characterized in that said aluminum-based catalyst is prepared according to an impregnation method comprising the following steps:
(1) weighing a certain amount of aluminum-containing compound, adding the aluminum-containing compound into soluble salt of a modification component, standing for 6-12 h, and then drying at 105-150 ℃ for 10-24 h, wherein the molar ratio of aluminum to the modification component is controlled to be 1: 0.01-0.3;
(2) roasting the substance prepared in the step (1) at the temperature of 300-800 ℃ for 2-6 h to obtain an aluminum-based catalyst precursor;
(3) and (3) tabletting and forming the precursor of the aluminum-based catalyst prepared in the step (2), then drying the precursor for 2-12 h at the temperature of 200-400 ℃ by using inert gas, and finally carrying out fluorination treatment for 10-24 h at the temperature of 150-400 ℃ to obtain the aluminum-based catalyst.
5. The aluminum-based catalyst according to claim 4, characterized in that the aluminum-containing compound is selected from the group consisting of aluminum oxide, halogenated aluminum oxide or oxyhalogen aluminum oxide and the soluble salt of the modifying component is selected from the group consisting of soluble nitrate salt of the modifying component, soluble sulfate salt of the modifying component or soluble chloride salt of the modifying component.
6. Process for the preparation of vinyl fluoride by gas phase dehydrofluorination of 1, 1-difluoroethane according to claim 1, characterized in that said aluminum-based catalyst is prepared according to a blending process comprising the following steps:
(1) weighing a certain amount of an aluminum-containing compound, a modified component metal simple substance, a modified component oxide or a modified component hydroxide, performing ball milling and blending to obtain a blend, wherein the molar ratio of aluminum to the modified component is controlled to be 1: 0.01-0.3;
(2) carrying out wet mixing extrusion forming on the blend prepared in the step (1), and roasting at the temperature of 300-800 ℃ for 2-6 h to obtain an aluminum-based catalyst precursor;
(3) and (3) drying the precursor of the aluminum-based catalyst prepared in the step (2) by using inert gas at the temperature of 200-400 ℃ for 2-12 h, and then carrying out fluorination treatment at the temperature of 150-400 ℃ for 10-24 h to obtain the aluminum-based catalyst.
7. The process for the vapor phase dehydrofluorination of 1, 1-difluoroethane to produce vinyl fluoride according to claim 6, wherein said aluminum-containing compound is selected from the group consisting of aluminum oxide, aluminum hydroxide, halogenated aluminum oxide, hydrated halogenated aluminum oxide and halogenated aluminum oxide.
8. The method for preparing vinyl fluoride by gas phase dehydrofluorination of 1, 1-difluoroethane according to claim 4 or 6, wherein the fluorination treatment in the step (3) is carried out by introducing a mixed gas consisting of HF and an inert gas in a molar ratio of 1: 4-10, and gradually increasing the concentration of HF in the mixed gas until the mixed gas finally introduced is pure hydrogen fluoride.
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| CN109174139B (en) * | 2018-08-16 | 2022-03-29 | 山东东岳化工有限公司 | Catalyst for preparing vinyl fluoride by removing HF from 1, 1-difluoroethane gas phase, and preparation method and application thereof |
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| US5880315A (en) * | 1996-11-21 | 1999-03-09 | E. I. Du Pont De Nemours And Company | Catalytic manufacture of vinyl fluoride |
| EP0946472B1 (en) * | 1996-11-21 | 2002-09-04 | E.I. Du Pont De Nemours And Company | The catalytic manufacture of vinyl fluoride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5880315A (en) * | 1996-11-21 | 1999-03-09 | E. I. Du Pont De Nemours And Company | Catalytic manufacture of vinyl fluoride |
| EP0946472B1 (en) * | 1996-11-21 | 2002-09-04 | E.I. Du Pont De Nemours And Company | The catalytic manufacture of vinyl fluoride |
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| 气相催化脱氟化氢制备含氟烯烃催化剂的研究进展;白彦波等;《化工进展》;20131231;第32卷(第10期);2387-2391 * |
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