CN101406835B - Hydrogenation and dechlorination catalyst - Google Patents
Hydrogenation and dechlorination catalyst Download PDFInfo
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- CN101406835B CN101406835B CN2008101824465A CN200810182446A CN101406835B CN 101406835 B CN101406835 B CN 101406835B CN 2008101824465 A CN2008101824465 A CN 2008101824465A CN 200810182446 A CN200810182446 A CN 200810182446A CN 101406835 B CN101406835 B CN 101406835B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000006298 dechlorination reaction Methods 0.000 title abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010306 acid treatment Methods 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 5
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002803 maceration Methods 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 5
- 238000006396 nitration reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 238000010574 gas phase reaction Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 8
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 7
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical class FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 1
- JYHHXQKTNJXLFU-UHFFFAOYSA-N C(C)Cl.[F] Chemical class C(C)Cl.[F] JYHHXQKTNJXLFU-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- -1 chloride hydrogen Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hydrogenation-dechlorination catalyst, which aims to solve the problem that the prior hydrogenation-dechlorination catalyst is low in activity and selectivity. The compositions in weight percentage of the catalyst are: 0.5 to 5 percent of Pd, 0.05 to 0.5 percent of Y, 0.05 to 0.5 percent of B and the balance being activated carbon subjected to acid treatment, wherein the activated carbon is coconut shell carbon, and the Pd, the Y and the B exist as elements or element oxides. The Pd, the Y and the B are loaded on the activated carbon subjected to the acid treatment by use of an impregnation method, and then the catalyst is obtained through drying, roasting, activation and other steps. The catalyst has the advantages of high activity, good selectivity and long service life, and is mainly used for preparing corresponding hydrofluorocarbon taking fluorochlorohydrocarbon as a raw material under gas-phase reaction conditions.
Description
Technical field
The present invention relates to a kind of Hydrodechlorinating catalyst, especially relate to and be used for the Hydrodechlorinating catalyst that the vapor phase method hydrogenation-dechlorination prepares freon substitute hydrogen fluorohydrocarbon.
Background technology
The widely used cold-producing medium of tradition, for example dichlorodifluoromethane (be called for short CFC-12), monochlorodifluoromethane (being called for short CFC-22) wait CFC, because of destroying the material of earth sky atmosphere ozone layer, and are limited by a series of international treaties or ban use of.Its main substitute is some not chloride hydrogen fluorohydrocarbons, as difluoromethane (being called for short HFC-32), 1,1,1, and 2-HFC-134a (being called for short HFC-134a), pentafluoroethane (being called for short HFC-125).Above-mentioned hydrogen fluorohydrocarbon is made by the fluorochlorohydrocarbon hydrogenation-dechlorination usually.
At present, the Hydrodechlorinating catalyst of fluorochlorohydrocarbon palladium carbon catalyst normally.For example Chinese patent CN11356550 discloses a kind of palladium-carbon catalyst, for improving the service life of catalyst, has added the S element in this catalyst, but 250 ℃ of catalysis pentafluorochloroethanes are made pentafluoroethane, operation is after 310 hours continuously, and conversion ratio is 46.9%, and selectivity is 83.0%.This catalyst still exist active and selectivity low, and the deficiency of lacking service life.
Summary of the invention
Technical problem to be solved by this invention is deficiency and the defective that overcomes the above-mentioned background technology, provide a kind of not only active high, selectivity is high, and the Hydrodechlorinating catalyst of long service life.
Design of the present invention: the present invention adds the B element in palladium-carbon catalyst, and the growing up of palladium crystal grain in the time of can hindering high temperature improved the stability of catalyst, effectively increases the service life of catalyst; The present invention adds Y element in palladium-carbon catalyst, can strengthen the absorption of halogenated alkane at catalyst surface, weaken the suction-operated of product HFCs at catalyst surface, thereby improve activity of such catalysts and selectivity, in addition, in the nitration mixture of boiling, active carbon is carried out acid treatment, adjust the structure of activated carbon surface functional group, can increase the micropore ratio of active carbon, thereby increase the specific area of active carbon.
The invention provides a kind of Hydrodechlorinating catalyst, the mass percent of this catalyst consists of Pd:0.5%-5%, Y:0.05%-0.5%, B:0.05%-0.5%, surplus: the active carbon of acid treatment, Pd, Y and B exist with element or element oxide, wherein active carbon is the coconut husk charcoal, and its specific area is greater than 600m
2/ g, this catalyst obtains by being prepared as follows method:
(1) active carbon is added in the nitration mixture of 0.1mol/L nitric acid and 0.3mol/L hydrochloric acid, boiled 4-10 hour, filter, wash to pH value of filtrate be 5-7, the gained active carbon obtained the active carbon of acid treatment at 120 ℃ of dry 2-10 hours;
(2) with soluble salt and the boric acid of Pd, Y, be dissolved in water, regulator solution pH value is 4-6, makes maceration extract, and wherein Pd, Y soluble salt are nitrate, acetate or chlorate;
(3) at bath temperature 50-90 ℃, under the condition of negative pressure, the maceration extract that obtains in the step (2) is dripped to the active carbon that step (1) step obtains, kept after dropwising 1-10 hour, get catalyst precursor;
(4) with the catalyst precursor that obtains in the step (3) under nitrogen protection; temperature 100-200 ℃ dry 2-10 hour; be warming up to then 250-350 ℃ of roasting 2-10 hour, again with nitrogen and hydrogen mol ratio be 4: 1 mist 200-300 ℃ the activation 2-20 hour, make catalyst.
Among the present invention, the mass percent preferred group of Hydrodechlorinating catalyst becomes Pd:2%, Y:0.3%, B:0.3%, surplus: the active carbon of acid treatment, Pd, Y and B exist with element or element oxide, and wherein active carbon is the coconut husk charcoal, and its specific area is greater than 600m
2/ g.
The preparation method of Hydrodechlorinating catalyst of the present invention may further comprise the steps:
(1) active carbon is added in the nitration mixture of 0.1N nitric acid and 0.3N hydrochloric acid, boiled 4-10 hour, filter, wash to pH value of filtrate be 5-7, the gained active carbon obtained the active carbon of acid treatment at 120 ℃ of dry 2-10 hours;
(2) with soluble salt and the boric acid of Pd, Y, be dissolved in water, use 0.1M hydrochloric acid conditioning solution pH value to be 4-6, make maceration extract, wherein Pd, Y soluble salt are nitrate, acetate or chlorate;
(3) at bath temperature 50-90 ℃, under the condition of negative pressure, the maceration extract that obtains in the step (2) is dripped to the active carbon that step (1) step obtains, kept after dropwising 1-10 hour, get catalyst precursor;
(4) with the catalyst precursor that obtains in the step (3) under nitrogen protection; temperature 100-200 ℃ dry 2-10 hour; be warming up to then 250-350 ℃ of roasting 2-10 hour, again with nitrogen and hydrogen mol ratio be 4: 1 mist 200-300 ℃ the activation 2-20 hour, make catalyst.
Hydrodechlorinating catalyst of the present invention is used for that the CFC catalytic hydrogenation and dechlorination prepares serial HFCs under the gas phase condition.For example, dicholorodifluoromethane, five fluorine monochlorethanes, 1,1-two chloro-1,2,2,2-HFC-134a or 1,2,2,2-tetrafluoro monochlorethane catalytic hydrogenation and dechlorination respectively prepares HFC-32, HFC-125 or HFC-134a.
The present invention compared with prior art, have following advantage: Hydrodechlorinating catalyst of the present invention is used for the reaction of the synthetic HFCs of catalysis CFC hydrogenation-dechlorination, this catalyst moves 1000 hours continuously, its conversion ratio and selectivity still are more than 97%, not only activity is high, selectivity is high, and long service life.
The specific embodiment
The present invention is described in more detail below by embodiment, but be not limited to given example.
The preparation acid treatment active carbon: with a certain amount of 4-8 order, specific surface greater than 600m
2The cocoanut active charcoal of/g boiled 4-10 hour with the nitration mixture of 0.1mol/L nitric acid and 0.3mol/L hydrochloric acid, filtered then, spent deionised water to pH5-7, and is standby in 120 ℃ of dry 2-10 hours.
Embodiment 1
Mass percent by catalyst consists of Pd:2%; Y:0.3%; B:0.3%; Surplus: the active carbon of acid treatment is implemented.
Configuration maceration extract: take by weighing Pd (NO
3)
24.446 gram, Y (NO
3)
36H
2O 1.327 grams, B (OH)
31.762 gram is dissolved in the 150ml deionized water, uses 0.1M watery hydrochloric acid regulator solution pH value to be 4-6, makes maceration extract.
The active carbons that take by weighing 100 gram acid treatments add in the rotary evaporator, and bath temperature 50-90 ℃, rotary speed 40-400 commentaries on classics/min, negative pressure slowly splashes into maceration extract from the dnockout mouth of rotary evaporator to absorbent charcoal carrier, distills simultaneously to remove H
2O kept after dropwising 2 hours, obtained catalyst precursor.This catalyst precursor is added reactor, at N
2100-200 ℃ of drying is 4 hours in the atmosphere, again at N
2250-350 ℃ of roasting is 4 hours in the atmosphere, then at N
2And H
2Mol ratio is 200-300 ℃ of activation 10 hours in 4: 1 the mist, makes catalyst, and Pd, Y and B exist with element or element oxide.
Embodiment 2
Mass percent by catalyst consists of Pd:0.5%; Y:0.5%; B:0.5%; Surplus: the active carbon of acid treatment is implemented, and catalyst preparation process is substantially the same manner as Example 1.
Embodiment 3
Mass percent by catalyst consists of Pd:1%; Y:0.4%; B:0.4%; Surplus: the active carbon of acid treatment is implemented, and catalyst preparation process is substantially the same manner as Example 1.
Embodiment 4
Mass percent by catalyst consists of Pd:5%; Y:0.05%; B:0.05%; Surplus: the active carbon of acid treatment is implemented, and catalyst preparation process is substantially the same manner as Example 1.
Embodiment 5
Mass percent by catalyst consists of Pd:2%; Y:0.3%; B:0.3%; Surplus: the active carbon of acid treatment is implemented, and adopts PdCl
2, YCl
36H
2O and B (OH)
3The preparation maceration extract.
The active carbon that takes by weighing 100 gram acid treatments adds and has in dropping funel and the churned mechanically there-necked flask, bath temperature 50-90 ℃, under negative pressure and stirring condition, slowly splash into maceration extract from dropping funel to absorbent charcoal carrier, kept after dropwising 2 hours, obtain catalyst precursor, condition of negative pressure can be realized by water circulating pump or oil pump.This catalyst precursor is added reactor, at N
2100-200 ℃ of drying is 4 hours in the atmosphere, again at N
2250-350 ℃ of roasting is 4 hours in the atmosphere, then at N
2And H
2Mol ratio is 200-300 ℃ of activation 10 hours in 4: 1 the mist, makes catalyst, and Pd, Y and B exist with element or element oxide.
Embodiment 6
Mass percent by catalyst consists of Pd:2%; Y:0.3%; B:0.3%; Surplus: the active carbon of acid treatment is implemented, and adopts Pd (CH
3COO)
2, Y (CH
3COO)
34H
2O, B (OH)
3The preparation maceration extract.Catalyst preparation process is substantially the same manner as Example 5.
Application examples 1
With the catalyst 40ml of the embodiment 1 preparation internal diameter 2cm that packs into, in the reaction tube of the SUS316 system of long 60cm, be used for the reaction of following synthesizing series HFCs:
Product is removed the laggard promoting the circulation of qi analysis of hplc of HCl and HF through washing and alkali cleaning, and the result is as shown in table 1.
Table 1
Selectivity is meant the ratio of target product, refers to generate the selectivity summation of HCFC-124, HFC-134a for reaction (3), and other reactions are the simple target product selectivity.
Application examples 2
The catalyst of embodiment 2 preparation is used for the reaction of synthesizing series HFCs, and application conditions and application examples 1 are basic identical, and the result is as shown in table 2.
Table 2
Selectivity is meant the ratio of target product, refers to generate the selectivity summation of HCFC-124, HFC-134a for reaction (3), and other reactions are the simple target product selectivity.
Application examples 3
The catalyst of embodiment 3 preparation is used for the reaction of synthesizing series HFCs, and application conditions and application examples 1 are basic identical, and the result is as shown in table 3.
Table 3
Selectivity is meant the ratio of target product, refers to generate the selectivity summation of HCFC-124, HFC-134a for reaction (3), and other reactions are the simple target product selectivity.
Application examples 4
The catalyst of embodiment 4 preparation is used for the reaction of synthesizing series HFCs, and application conditions and application examples 1 are basic identical, and the result is as shown in table 4.
Table 4
Selectivity is meant the ratio of target product, refers to generate the selectivity summation of HCFC-124, HFC-134a for reaction (3), and other reactions are the simple target product selectivity.
Application examples 5
The catalyst of embodiment 5 preparation is used for the reaction of synthesizing series HFCs, and application conditions and application examples 1 are basic identical, and the result is as shown in table 5.
Table 5
Selectivity is meant the ratio of target product, refers to generate the selectivity summation of HCFC-124, HFC-134a for reaction (3), and other reactions are the simple target product selectivity.
Application examples 6
The catalyst of embodiment 6 preparation is used for the reaction of synthesizing series HFCs, and application conditions and application examples 1 are basic identical, and the result is as shown in table 6.
Table 6
Selectivity is meant the ratio of target product, refers to generate the selectivity summation of HCFC-124, HFC-134a for reaction (3), and other reactions are the simple target product selectivity.
Claims (2)
1. Hydrodechlorinating catalyst, the mass percent that it is characterized in that this catalyst consists of Pd:0.5%-5%, Y:0.05%-0.5%, B:0.05%-0.5%, surplus: the active carbon of acid treatment, Pd, Y and B exist with element or element oxide, wherein active carbon is the coconut husk charcoal, and its specific area is greater than 600m
2/ g, this catalyst obtains by being prepared as follows method:
(1) active carbon is added in the nitration mixture of 0.1mol/L nitric acid and 0.3mol/L hydrochloric acid, boiled 4-10 hour, filter, wash to pH value of filtrate be 5-7, the gained active carbon obtained the active carbon of acid treatment at 120 ℃ of dry 2-10 hours;
(2) with Pd, Y soluble salt and boric acid, be dissolved in water, regulator solution pH value is 4-6, makes maceration extract, and wherein Pd, Y soluble salt are nitrate, acetate or chlorate;
(3) at bath temperature 50-90 ℃, under the condition of negative pressure, the maceration extract that obtains in the step (2) is dripped to the active carbon that step (1) obtains, kept after dropwising 1-10 hour, get catalyst precursor;
(4) with the catalyst precursor that obtains in the step (3) under nitrogen protection; temperature 100-200 ℃ dry 2-10 hour; be warming up to then 250-350 ℃ of roasting 2-10 hour, again with nitrogen and hydrogen mol ratio be 4: 1 mist 200-300 ℃ the activation 2-20 hour, make catalyst.
2. Hydrodechlorinating catalyst according to claim 1, it is characterized in that the mass percent of this catalyst consists of Pd:2%, Y:0.3%, B:0.3%, surplus: the active carbon of acid treatment, Pd, Y and B exist with element or element oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101824465A CN101406835B (en) | 2008-12-08 | 2008-12-08 | Hydrogenation and dechlorination catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101824465A CN101406835B (en) | 2008-12-08 | 2008-12-08 | Hydrogenation and dechlorination catalyst |
Publications (2)
| Publication Number | Publication Date |
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| CN101406835A CN101406835A (en) | 2009-04-15 |
| CN101406835B true CN101406835B (en) | 2011-05-25 |
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ID=40570156
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|---|---|---|---|
| CN2008101824465A Expired - Fee Related CN101406835B (en) | 2008-12-08 | 2008-12-08 | Hydrogenation and dechlorination catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101632931B (en) * | 2009-08-14 | 2012-06-27 | 西安近代化学研究所 | Hydrodechlorination catalyst |
| CN103418367B (en) * | 2013-07-12 | 2015-10-28 | 西安近代化学研究所 | A kind of catalyst and preparation method preparing Fluorine containing olefine for chlorofluoro-alkane |
| CN109513452B (en) * | 2018-11-29 | 2019-10-18 | 东莞东阳光科研发有限公司 | Film catalyst, its presoma and carrier and preparation method thereof |
| CN110327922A (en) * | 2019-07-30 | 2019-10-15 | 苏州卡泰里环保能源有限公司 | A kind of catalyst for catalytic combustion and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005019142A1 (en) * | 2003-08-13 | 2005-03-03 | Great Lakes Chemical Corporation | Systems and methods for producing fluorocarbons |
| CN101007280A (en) * | 2007-01-26 | 2007-08-01 | 南开大学 | Preparation method of a novel hydrogenation and dechlorination catalyst |
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2008
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005019142A1 (en) * | 2003-08-13 | 2005-03-03 | Great Lakes Chemical Corporation | Systems and methods for producing fluorocarbons |
| CN101007280A (en) * | 2007-01-26 | 2007-08-01 | 南开大学 | Preparation method of a novel hydrogenation and dechlorination catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 冯雪涛,吕剑.负载型加氢脱氯合成HFCs催化剂的研究进展.《工业催化》.2003,第11卷(第8期),1-7. * |
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