CN113769765A - Bimetallic sulfate composite catalyst and preparation method and application thereof - Google Patents
Bimetallic sulfate composite catalyst and preparation method and application thereof Download PDFInfo
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- CN113769765A CN113769765A CN202111159267.1A CN202111159267A CN113769765A CN 113769765 A CN113769765 A CN 113769765A CN 202111159267 A CN202111159267 A CN 202111159267A CN 113769765 A CN113769765 A CN 113769765A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 114
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 11
- 229910052745 lead Inorganic materials 0.000 claims abstract description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical group CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 claims description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 29
- 230000032683 aging Effects 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000000967 suction filtration Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 239000011737 fluorine Substances 0.000 claims description 19
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 13
- 229910052788 barium Inorganic materials 0.000 claims description 12
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 229910001626 barium chloride Inorganic materials 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 43
- -1 sulfate compound Chemical class 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 19
- 238000011049 filling Methods 0.000 description 19
- 238000004321 preservation Methods 0.000 description 19
- 238000012216 screening Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910009523 YCl3 Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a bimetallic sulfate composite catalyst, a preparation method and application thereof, wherein the composite catalyst is BaSO4The bimetallic sulfate composite catalyst is prepared by taking sulfate of any one of Pb, Ag, Y, Sr, Ca and Ni as a main catalyst and adopting a coprecipitation method. The bimetallic sulfate composite catalyst of the invention is applied to the reaction of preparing fluoroolefins (HFOs) by removing HCl from the gas phase of fluorochloroalkane (HCFCs), has extremely high selectivity and stability, and catalyzesThe chemical selectivity is higher than 90%, the catalytic conversion rate reaches more than 80%, and the catalyst has the advantages of low reaction temperature, high conversion rate, high selectivity, good stability, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of heterogeneous thermal catalysts, and particularly relates to a bimetallic sulfate composite catalyst and a preparation method and application thereof.
Background
1, 1-difluoro-1-chloroethane (HCFC-142b) is a compound of formula CF2ClCH3The Hydrochlorofluorocarbons (HCFCs) of (1) are the most important industrial raw materials for producing polyvinylidene fluoride (PVDF) monomer vinylidene fluoride (VDF). Since the early 1990 s, the content of HCFC-142b in the atmosphere is steadily increasing, the high potential value of greenhouse effect of HCFC-142b can pollute the atmospheric environment, and the HCFC-142b can be used as a raw material to produce polyvinylidene fluoride so as to realize resource conversion.
The temperature of HCFC-142b thermal cracking is generally 600-800 ℃, carbon deposition coking, side reactions and disproportionation are easily caused, and the yield of a target product VDF is influenced. The addition of the catalyst can reduce the reaction energy barrier of HCFC-142b dehydrochlorination, greatly reduce the temperature required by the reaction, and is an effective and environment-friendly way for producing VDF at present. At present, various defects exist in catalysts for removing HCl by catalytic cracking HCFC-142b, such as the activated carbon catalyst is easy to be activated and difficult to regenerate; the metal oxide is easy to react with hydrogen chloride to be quickly deactivated; the metal fluoride preferentially selects to remove HF, so that the reaction selectivity is reduced; and the metal chloride does not react with hydrogen chloride but has poor activity, so the development of a high-selectivity catalyst resistant to chlorination in the reaction has important significance.
For the reaction of preparing fluoroolefins (HFOs) by removing HCl from gas phase of fluorine-containing chloroalkane (HCFCs), the affinity of the main catalyst metal to Cl element has important influence on the reaction selectivity and the conversion activity. BaSO4Has strong affinity or selective adsorption to Cl, thereby having high selectivity to main product vinylidene fluoride (VDF)But poor stability. By doping other metals with high activity and stability, solid solution can be formed, the interaction between metals is enhanced, the aim of simultaneously having high activity and high selectivity is further achieved, and the method has good application prospect in the field of selective dehydrochlorination.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a bimetallic sulfate compound catalyst and a preparation method and application thereof. The composite catalyst disclosed by the invention is applied to preparation of vinylidene fluoride by catalytic cracking of HCl from 1, 1-difluoro-1-chloroethane, and has the advantages of low reaction temperature, high catalytic conversion rate, high catalytic selectivity, good catalytic stability, low catalyst cost and the like.
The bimetallic sulfate composite catalyst is characterized in that the composite catalyst is BaSO4The bimetallic sulfate composite catalyst uses sulfate of any one of Pb, Ag, Y, Sr, Ca and Ni as a catalyst promoter.
The preparation method of the bimetallic sulfate composite catalyst is characterized by being prepared by a coprecipitation method and comprising the following steps of:
1) dissolving a barium source and a cocatalyst precursor into deionized water, stirring for 20-40 min, then dripping a water solution of a precipitator, and stirring for reaction for 2-4 h to obtain a precipitate mixture;
2) aging the precipitation mixture obtained in the step 1) at room temperature, then performing suction filtration, washing with water, and drying to obtain the bimetallic sulfate composite catalyst.
The preparation method of the bimetallic sulfate compound catalyst is characterized in that the barium source in the step 1) is one of barium nitrate, barium chloride or barium hydroxide, and barium nitrate is preferred.
The preparation method of the bimetallic sulfate composite catalyst is characterized in that in the step 1), the precursor of the promoter is one of nitrate, chloride or hydroxide of any one of Pb, Ag, Y, Sr, Ca and Ni, preferably nitrate of any one of Pb, Ag, Y, Sr, Ca and Ni, and more preferably nitrate of any one of Y, Sr, Ca and Ni.
The preparation method of the bimetallic sulfate composite catalyst is characterized in that in the step 1), the feeding molar ratio of metal elements in a promoter precursor to barium elements in a barium source is 0.01-2: 1, and preferably 0.1-1: 1.
The preparation method of the bimetallic sulfate composite catalyst is characterized in that in the step 1), the stirring reaction temperature is 10-70 ℃, and preferably 30-50 ℃.
The preparation method of the bimetallic sulfate composite catalyst is characterized in that in the step 1), the precipitator is one of ammonium sulfate, ammonium bisulfate or dilute sulfuric acid, and the feeding molar ratio of the precipitator to barium in a barium source is 1-2: 1, preferably 1.1-1.5: 1.
The preparation method of the bimetallic sulfate composite catalyst is characterized in that in the step 2), the aging time is 0.2-3 hours, preferably 0.5-1.5 hours; the drying temperature is 60-140 ℃, the drying time is 8-16 h, the preferred drying temperature is 90-110 ℃, and the preferred drying time is 11-13 h.
The bimetallic sulfate composite catalyst is applied to the reaction of catalyzing gas phase HCl removal of fluorine-containing chloroalkane to prepare fluorine-containing olefin.
Further, the fluorine-containing chloroalkane is 1, 1-difluoro-1-chloroethane, and the fluorine-containing olefin is vinylidene fluoride; the process of applying the bimetallic sulfate composite catalyst to the reaction of catalyzing the gas phase of fluorine-containing chloroalkane to remove HCl to prepare fluorine-containing olefin is as follows: the catalyst is filled into a fixed bed reactor, and N is introduced2And a mixed gas containing a fluorine-containing chloroalkane, N2And the fluorine-containing chloroalkane in a volume ratio of 1: 0.5-2, N2The total space velocity of the mixed gas containing the fluorine-containing chloroalkane is 250-300 h-1And reacting at 350-450 ℃ to generate a vinylidene fluoride product.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
the bimetallic sulfate composite catalyst is obtained by doping a cocatalyst, such as sulfate of any one of Y, Sr, Ca and Ni as the cocatalyst, and combines the high conversion rate of Ba salt with the high selectivity and the anti-chlorination effect of M metal salt, so that the catalyst has the anti-chlorination effect, the problems of carbon deposition and inactivation of activated carbon, metal oxide and metal fluoride catalyst are solved, and the activity, selectivity and stability of the bimetallic sulfate composite catalyst are improved. The obtained bimetallic sulfate composite catalyst is used for preparing vinylidene fluoride by catalytic cracking of 1, 1-difluoro-1-chloroethane to remove HCl, and the catalyst is found to have the advantages of low reaction temperature, good catalytic stability, high selectivity and the like.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
0.040mol of Ba (NO)3)2And 0.040mol of Pb (NO)3)2Dissolving in 200mL deionized water at 50 deg.C, stirring in water bath for 40min, and adding 200mL of 0.600mol/L (NH)4)2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 50 ℃ for 4h, then aging at room temperature for 1.5h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 110 ℃ for 11h to obtain a catalyst sample, tabletting, and then screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction formula is as follows:
CF2ClCH3→CF2＝CH2+HCl
the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 1.
Example 2
0.040mol of Ba (NO)3)2And 0.020mol of Pb (NO)3)2Dissolving in 150mL deionized water at 40 deg.C, stirring in water bath for 30min, and adding 150mL of 0.520mol/L NH dropwise4HSO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 40 ℃ for 3h, then aging at room temperature for 1h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 100 ℃ for 12h to obtain a catalyst sample, and carrying out tabletting and screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 1.
Example 3
0.040mol of Ba (NO)3)2And 0.004mol of Pb (NO)3)2Dissolving in 110mL deionized water at 30 deg.C, stirring in water bath for 20min, and adding 110mL 0.440mol/L diluted H dropwise2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 30 ℃ for 2h, then aging at room temperature for 0.5h, then carrying out suction filtration, washing with water for 3 times, then placing into an oven for drying at 90 ℃ for 13h to obtain a catalyst sample, and sieving by using a 20-40-mesh sample sieve after tabletting.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. The reaction is carried out for 30 hours and the sample is dividedThe evaluation results are shown in table 1.
TABLE 1 conversion of HCFC-142b and VDF selectivity for catalysts with different Pb contents
Example 4
0.040mol of Ba (NO)3)2And 0.040mol AgNO3Dissolving in 200mL deionized water at 50 deg.C, stirring in water bath for 40min, and adding 150mL of 0.600mol/L (NH)4)2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 50 ℃ for 4h, then aging at room temperature for 1.5h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 110 ℃ for 11h to obtain a catalyst sample, tabletting, and then screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 2.
Example 5
0.040mol of Ba (NO)3)2And 0.020mol AgNO3Dissolving in 150mL deionized water at 40 deg.C, stirring in water bath for 30min, and adding 125mL of 0.520mol/L NH dropwise4HSO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 40 ℃ for 3h, then aging at room temperature for 1h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 100 ℃ for 12h to obtain a catalyst sample, and carrying out tabletting and screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, and the filling amount of the catalyst is 2mL, introduction of N2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 2.
Example 6
0.040mol of Ba (NO)3)2And 0.004molAgNO3Dissolving in 110mL deionized water at 30 deg.C, stirring in water bath for 20min, and adding 105mL 0.440mol/L diluted H dropwise2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 30 ℃ for 2h, then aging at room temperature for 0.5h, then carrying out suction filtration, washing with water for 3 times, then placing into an oven for drying at 90 ℃ for 13h to obtain a catalyst sample, and sieving by using a 20-40-mesh sample sieve after tabletting.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 2.
TABLE 2 conversion and VDF selectivity of HCFC-142b catalysts with different Ag contents
The experimental results of comparative examples 1 to 6 show that: Ba-Pb bimetallic sulfate or Ba-Ag bimetallic sulfate is used as a catalyst to continuously evaluate the reaction for 30 hours, although the conversion rate of the catalytic reaction is general, the catalytic selectivity is high and reaches more than 96 percent, and a better reaction effect is obtained.
Example 7
0.040mol of Ba (NO)3)2And 0.040mol of Y (NO)3)3·6H2O dissolved in 200mL deionized water at 50 deg.CIn the process, the mixture is stirred for 40min in a water bath, and 250mL of (NH) with the concentration of 0.600mol/L is added dropwise4)2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 50 ℃ for 4h, then aging at room temperature for 1.5h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 110 ℃ for 11h to obtain a catalyst sample, tabletting, and then screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 3.
Example 8
0.040mol of BaCl2·2H2O and 0.020mol YCl3·6H2Dissolving O in 150mL deionized water at 40 deg.C, stirring in water bath for 30min, and adding 175mL of 0.520mol/L NH dropwise4HSO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 40 ℃ for 3h, then aging at room temperature for 1h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 100 ℃ for 12h to obtain a catalyst sample, and carrying out tabletting and screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 3.
Example 9
0.040mol of Ba (NO)3)2And 0.004mol of Y (NO)3)3·6H2Dissolving O in 110mL deionized water at 30 ℃, and stirring in water bath for 20min, then 115mL of 0.440mol/L dilute H is added dropwise2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 30 ℃ for 2h, then aging at room temperature for 0.5h, then carrying out suction filtration, washing with water for 3 times, then placing into an oven for drying at 90 ℃ for 13h to obtain a catalyst sample, and sieving by using a 20-40-mesh sample sieve after tabletting.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 3.
TABLE 3 conversion and VDF selectivity of HCFC-142b catalysts with different Y content
Example 10
0.040mol of Ba (NO)3)2And 0.040mol of Sr (NO)3)2Dissolving in 200mL deionized water at 50 deg.C, stirring in water bath for 40min, and adding 200mL of 0.600mol/L (NH)4)2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 50 ℃ for 4h, then aging at room temperature for 1.5h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 110 ℃ for 11h to obtain a catalyst sample, tabletting, and then screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. Reaction for 30h, sampling and analyzingThe evaluation results are shown in Table 4.
Example 11
0.040mol of BaCl2·2H2O and 0.020mol SrCl2·6H2Dissolving O in 150mL deionized water at 40 deg.C, stirring in water bath for 30min, and adding 150mL of 0.520mol/L NH dropwise4HSO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 40 ℃ for 3h, then aging at room temperature for 1h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 100 ℃ for 12h to obtain a catalyst sample, and carrying out tabletting and screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 4.
Example 12
0.040mol of Ba (OH)28H2O and 0.004mol Sr (OH)2Dissolving in 110mL deionized water at 30 deg.C, stirring in water bath for 20min, and adding 110mL 0.440mol/L diluted H dropwise2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 30 ℃ for 2h, then aging at room temperature for 0.5h, then carrying out suction filtration, washing with water for 3 times, then placing into an oven for drying at 90 ℃ for 13h to obtain a catalyst sample, and sieving by using a 20-40-mesh sample sieve after tabletting.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 4.
TABLE 4 conversion and VDF selectivity of HCFC-142b catalyst with different Sr content
Example 13
0.040mol of Ba (NO)3)2And 0.040mol of Ca (NO)3)2·4H2Dissolving O in 200mL deionized water at 50 deg.C, stirring in water bath for 40min, and adding 200mL of 0.600mol/L (NH)4)2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 50 ℃ for 4h, then aging at room temperature for 1.5h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 110 ℃ for 11h to obtain a catalyst sample, tabletting, and then screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 5.
Example 14
0.040mol of BaCl2·2H2O and 0.020mol of CaCl2Dissolving in 150mL deionized water at 40 deg.C, stirring in water bath for 30min, and adding 150mL of 0.520mol/L NH dropwise4HSO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 40 ℃ for 3h, then aging at room temperature for 1h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 100 ℃ for 12h to obtain a catalyst sample, and carrying out tabletting and screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2And HCFC-142b, N, of a mixed gas2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 5.
Example 15
0.040mol of Ba (NO)3)2And 0.004mol of Ca (NO)3)2Dissolving in 110mL deionized water at 30 deg.C, stirring in water bath for 20min, and adding 110mL 0.440mol/L diluted H dropwise2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 30 ℃ for 2h, then aging at room temperature for 0.5h, then carrying out suction filtration, washing with water for 3 times, then placing into an oven for drying at 90 ℃ for 13h to obtain a catalyst sample, and sieving by using a 20-40-mesh sample sieve after tabletting.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 5.
TABLE 5 conversion of HCFC-142b and VDF selectivity for catalysts with different Ca contents
Example 16
0.040mol of BaCl2And 0.040mol of Ni (NO)3)2·6H2Dissolving O in 200mL deionized water at 50 deg.C, stirring in water bath for 40min, and adding 200mL of 0.600mol/L (NH)4)2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 50 ℃ for 4h, then aging at room temperature for 1.5h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 110 ℃ for 11h to obtain a catalyst sample, tabletting, and then screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 6.
Example 17
0.040mol of BaCl2·2H2O and 0.020mol NiCl2·6H2Dissolving O in 150mL deionized water at 40 deg.C, stirring in water bath for 30min, and adding 150mL of 0.520mol/L NH dropwise4HSO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 40 ℃ for 3h, then aging at room temperature for 1h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 100 ℃ for 12h to obtain a catalyst sample, and carrying out tabletting and screening by using a 20-40-mesh sample separating sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 6.
Example 18
0.040mol of BaCl2And 0.004mol of Ni (NO)3)2·6H2Dissolving O in 110mL deionized water at 30 deg.C, stirring in water bath for 20min, and adding 110mL 0.440mol/L diluted H dropwise2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 30 ℃ for 2h, then aging at room temperature for 0.5h, then carrying out suction filtration, washing with water for 3 times, then placing into an oven for drying at 90 ℃ for 13h to obtain a catalyst sample, and sieving by using a 20-40-mesh sample sieve after tabletting.
The bimetallic sulfuric acid prepared by the methodThe salt composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 400 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 6.
TABLE 6 conversion and VDF selectivity of HCFC-142b catalysts with different Ni content
The results of the experiments of comparative examples 7 to 18 show that: when sulfate of any one of Y, Sr, Ca and Ni is taken as a cocatalyst, the VDF selectivity of the catalytic reaction is basically kept above 90% and the catalytic conversion rate can reach above 80% when the reaction is continuously evaluated for 30 hours, so that a good technical effect is achieved.
Example 19
0.040mol of Ba (NO)3)2Dissolving in 100mL deionized water at 40 deg.C, stirring in water bath for 30min, and adding 100mL 0.400mol/L (NH)4)2SO4And (3) carrying out heat preservation and stirring reaction on the aqueous solution at 40 ℃ for 3h, then aging at room temperature for 1h, then carrying out suction filtration, washing with water for 3 times, then putting into an oven for drying at 90 ℃ for 12h to obtain a catalyst sample, tabletting, and then screening by using a 20-40-mesh sample separation sieve.
The prepared bimetallic sulfate composite catalyst is used for catalyzing 1, 1-difluoro-1-chloroethane (HCFC-142b) to crack to prepare 1, 1-difluoroethylene (VDF), and the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas with HCFC-142b, N2Flow 5mL/min, HCFC-142b flow 5mL/min, N2The total space velocity of the mixed gas with HCFC-142b is 300h-1The reaction temperature was 425 ℃. A sample was taken after 30 hours of reaction and analyzed, and the evaluation results are shown in Table 7.
TABLE 7
From the experimental results of example 19, it can be seen that: directly using BaSO4When the catalyst is used, the catalytic selectivity is still kept high when the reaction is continuously evaluated for 30 hours, but the conversion rate is only 56.3 percent, and the catalytic effect is not ideal.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. The bimetallic sulfate composite catalyst is characterized in that the composite catalyst is BaSO4The bimetallic sulfate composite catalyst uses sulfate of any one of Pb, Ag, Y, Sr, Ca and Ni as a catalyst promoter.
2. The method for preparing the bimetallic sulfate complex catalyst according to claim 1, wherein the bimetallic sulfate complex catalyst is prepared by a coprecipitation method, and the method comprises the following steps:
1) dissolving a barium source and a cocatalyst precursor into deionized water, stirring for 20-40 min, then dripping a water solution of a precipitator, and stirring for reaction for 2-4 h to obtain a precipitate mixture;
2) aging the precipitation mixture obtained in the step 1) at room temperature, then performing suction filtration, washing with water, and drying to obtain the bimetallic sulfate composite catalyst.
3. The method for preparing a bimetallic sulfate composite catalyst according to claim 2, wherein the barium source in step 1) is one of barium nitrate, barium chloride or barium hydroxide, preferably barium nitrate.
4. The method of claim 2, wherein the promoter precursor in step 1) is one of nitrate, chloride or hydroxide of any one of Pb, Ag, Y, Sr, Ca and Ni, preferably nitrate of any one of Pb, Ag, Y, Sr, Ca and Ni, and more preferably nitrate of any one of Y, Sr, Ca and Ni.
5. The method for preparing the bimetallic sulfate composite catalyst according to claim 2, wherein in the step 1), the feeding molar ratio of the metal element in the promoter precursor to the barium element in the barium source is 0.01-2: 1, preferably 0.1-1: 1.
6. The method for preparing the bimetallic sulfate composite catalyst according to claim 2, wherein in the step 1), the stirring reaction temperature is 10-70 ℃, preferably 30-50 ℃.
7. The preparation method of the bimetallic sulfate composite catalyst as in claim 2, wherein in the step 1), the precipitant is one of ammonium sulfate, ammonium bisulfate or dilute sulfuric acid, and the feeding molar ratio of the precipitant to barium in the barium source is 1-2: 1, preferably 1.1-1.5: 1.
8. The preparation method of the bimetallic sulfate composite catalyst as in claim 2, wherein in the step 2), the aging time is 0.2-3 hours, preferably 0.5-1.5 hours; the drying temperature is 60-140 ℃, the drying time is 8-16 h, the preferred drying temperature is 90-110 ℃, and the preferred drying time is 11-13 h.
9. The use of the bimetallic sulfate composite catalyst of claim 1 in catalyzing the reaction of removing HCl from a gas phase of fluorine-containing chloroalkane to prepare fluorine-containing olefin.
10. The use of claim 9, wherein the fluorine-containing chloroalkane is 1, 1-difluoro-1-chloroethane and the fluorine-containing olefin is vinylidene fluoride(ii) a The process of applying the bimetallic sulfate composite catalyst to the reaction of catalyzing the gas phase of fluorine-containing chloroalkane to remove HCl to prepare fluorine-containing olefin is as follows: the catalyst is filled into a fixed bed reactor, and N is introduced2And a mixed gas containing a fluorine-containing chloroalkane, N2And the fluorine-containing chloroalkane in a volume ratio of 1: 0.5-2, N2The total space velocity of the mixed gas containing the fluorine-containing chloroalkane is 250-300 h-1And reacting at 350-450 ℃ to generate a vinylidene fluoride product.
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Citations (4)
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| GB562696A (en) * | 1943-01-07 | 1944-07-12 | Hardwicke Slingsby Tasker | Improvements in the production of fluorescent materials |
| CN1262144A (en) * | 1998-10-13 | 2000-08-09 | 底古萨－胡尔斯股份公司 | Nitrogen oxide storing catalyst |
| JP2000325790A (en) * | 1999-05-21 | 2000-11-28 | Tanaka Kikinzoku Kogyo Kk | Sulfide oxidizing catalyst and sulfide concentration measuring device using this catalyst |
| CN106588563A (en) * | 2016-12-28 | 2017-04-26 | 浙江工业大学 | Preparation method of 1,1-difluoroethylene |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB562696A (en) * | 1943-01-07 | 1944-07-12 | Hardwicke Slingsby Tasker | Improvements in the production of fluorescent materials |
| CN1262144A (en) * | 1998-10-13 | 2000-08-09 | 底古萨－胡尔斯股份公司 | Nitrogen oxide storing catalyst |
| JP2000325790A (en) * | 1999-05-21 | 2000-11-28 | Tanaka Kikinzoku Kogyo Kk | Sulfide oxidizing catalyst and sulfide concentration measuring device using this catalyst |
| CN106588563A (en) * | 2016-12-28 | 2017-04-26 | 浙江工业大学 | Preparation method of 1,1-difluoroethylene |
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