CN101015803A - 一种催化剂及制备方法及在四氯化碳加氢脱氯的用途 - Google Patents
一种催化剂及制备方法及在四氯化碳加氢脱氯的用途 Download PDFInfo
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- CN101015803A CN101015803A CN 200710020016 CN200710020016A CN101015803A CN 101015803 A CN101015803 A CN 101015803A CN 200710020016 CN200710020016 CN 200710020016 CN 200710020016 A CN200710020016 A CN 200710020016A CN 101015803 A CN101015803 A CN 101015803A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000006298 dechlorination reaction Methods 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000002803 maceration Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims 5
- 238000006722 reduction reaction Methods 0.000 claims 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 18
- 230000000382 dechlorinating effect Effects 0.000 abstract 1
- 229940050176 methyl chloride Drugs 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000006227 byproduct 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
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000505 pernicious effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 102100024304 Protachykinin-1 Human genes 0.000 description 1
- 101800003906 Substance P Proteins 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- MVGLBXWFOSHCCP-UHFFFAOYSA-N chloroform;tetrachloromethane Chemical compound ClC(Cl)Cl.ClC(Cl)(Cl)Cl MVGLBXWFOSHCCP-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
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- 208000012839 conversion disease Diseases 0.000 description 1
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- 210000003278 egg shell Anatomy 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 239000002574 poison Substances 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
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- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
实施例 | 催化剂 | 还原条件 | 反应条件CCl4∶H2∶CH3OH=1∶6∶2.5 | ||||
温度(℃) | 时间(h) | 温度(℃) | 压力(atm) | 空速(h-1) | 进料摩尔比CCl4∶H2∶CH3OH | ||
6 | 0.5%Pt/Cr2O3-ZrO2 | 280 | 5 | 225 | 4 | 1200 | 1∶6∶2.5 |
7 | 0.5%Pt/Cr2O3-ZrO2 | 200 | 2 | 80 | 1 | 2000 | 1∶9∶5 |
8 | 0.5%Pt-10%NiO/Mn2O3-TiO2 | 500 | 2 | 100 | 3 | 1000 | 1∶2∶1.5 |
9 | 0.5%Pt/Cr2O3-TiO2 | 280 | 3 | 400 | 5 | 1200 | 1∶5∶5 |
10 | 0.5%Pt/Cr2O3-TiO2 | 280 | 2 | 150 | 8 | 2500 | 1∶6∶3 |
11 | 0.5%Pt-10%NiO/Cr2O3-TiO2 | 200 | 1 | 225 | 6 | 500h | 1∶1∶4 |
12 | 0.5%Pt-10%NiO/Cr2O3-TiO2 | 350 | 3 | 225 | 4 | 1200 | 1∶6∶2.5 |
13 | 20%NiO/ZnO-Al2O3 | 400 | 3 | 300 | 4 | 500 | 1∶6∶2.5 |
14 | 0.6%Pd/Fe2O3-ZrO2-TiO2 | 280 | 3 | 225 | 4 | 1200 | 1∶6∶2.5 |
实施例 | 四氯化碳 | 氯仿 | HCl | 一氯甲烷 | 二氯甲烷 | 甲醇 | 四氯化碳转化率 | 氯仿转化率 | HCl转化率 |
6 | 2.67% | 8.80% | 1.60% | 40.48% | 16.64% | 29.8% | 90.5% | 65.4% | 96.2% |
7 | 9.86% | 5.80% | 1.10% | 6.35% | 0.82% | 76.07% | 40.2% | 12.4% | 85.2% |
8 | 1.91% | 12.29% | 11.77% | 42.72% | 21.10% | 10.22% | 94.6% | 63.2% | 78.4% |
9 | 0.81% | 3.97% | 0.28% | 27.37% | 11.84% | 55.73% | 95.1% | 74.9% | 99.0% |
10 | 2.65% | 22.18% | 11.78% | 22.18% | 14.47% | 43.98% | 88.4% | 74.2% | 65.3% |
11 | 2.14% | 5.10% | 12.55% | 29.11% | 12.55% | 50.02% | 89.2% | 71.1% | 96.4% |
12 | 1.91% | 2.73% | 3.17% | 45.61% | 23.03% | 23.55% | 93.1% | 89.4% | 93.5% |
13 | 4.42% | 4.29%% | 0.22% | 43.67%% | 19.80% | 27.60% | 84.5% | 82.2% | 99.5% |
14 | 3.29% | 4.96% | 0.81% | 44.33% | 20.09% | 26.52% | 88.4% | 80.2% | 98.2% |
Claims (8)
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CN102441401A (zh) * | 2010-09-30 | 2012-05-09 | 财团法人工业技术研究院 | 选择性氧化一氧化碳的催化剂、其制造及使用方法 |
CN102633591A (zh) * | 2011-11-03 | 2012-08-15 | 常州大学 | 一种四氯化碳催化转化的工艺 |
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CN101362090B (zh) * | 2008-09-28 | 2013-04-10 | 江苏理文化工有限公司 | 一种用于将四氯化碳转化为氯仿的催化剂及其制备方法 |
CN103131488A (zh) * | 2011-11-30 | 2013-06-05 | 中国科学院大连化学物理研究所 | 一种低浓度甲烷催化燃烧的催化剂及其制备方法 |
CN103977795A (zh) * | 2014-06-05 | 2014-08-13 | 西安凯立化工有限公司 | 一种降解六氯苯的催化剂的制备方法 |
CN104646048A (zh) * | 2013-11-20 | 2015-05-27 | 中国石油化工股份有限公司 | 一种加氢催化剂的制备方法 |
CN105457651A (zh) * | 2014-09-05 | 2016-04-06 | 浙江蓝天环保高科技股份有限公司 | 一种加氢脱氯催化剂及其在三氟氯乙烯制备中的应用 |
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