CN112569932A - 一种高稳定性脱氯催化剂、制备方法及脱氯工艺 - Google Patents
一种高稳定性脱氯催化剂、制备方法及脱氯工艺 Download PDFInfo
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- CN112569932A CN112569932A CN202011450477.1A CN202011450477A CN112569932A CN 112569932 A CN112569932 A CN 112569932A CN 202011450477 A CN202011450477 A CN 202011450477A CN 112569932 A CN112569932 A CN 112569932A
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- Prior art keywords
- metal
- dechlorination
- catalyst
- metal layer
- high stability
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 92
- 239000002184 metal Substances 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 238000004873 anchoring Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 28
- 239000002243 precursor Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 2
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 2
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- GPAKJVMKNDXBHH-UHFFFAOYSA-N 2,3,6-trichloropyridine Chemical compound ClC1=CC=C(Cl)C(Cl)=N1 GPAKJVMKNDXBHH-UHFFFAOYSA-N 0.000 description 1
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- -1 carbon tetrachloride Chemical class 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
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Abstract
本发明涉及一种高稳定性脱氯催化剂、制备方法及脱氯工艺，所述催化剂包括炭载体、炭载体表面的第一金属层，以及与第一金属层锚定结合的第二金属层，第一金属层中的第一金属选自第IB、IIB、IVB、VIB、VIIB族金属中的一种或多种，第二金属层中的第二金属选自第VIII族金属中的一种或多种，第二金属在微波反应器中与第一金属锚定结合。本发明的脱氯催化剂具有稳定性高、转化率高、选择性高等优点，高稳定性脱氯催化剂的制备方法易于工业放大生产，脱氯工艺安全环保、生产率高。
Description
技术领域
本发明属于化工领域，具体涉及一种高稳定性脱氯催化剂、制备方法及脱氯工艺。
背景技术
脱氯是避免含氯化合物造成的环境污染问题、生产有价值的产物、实现资源化利用的重要方法。
CN110961110A公开了一种2,3,6-三氯吡啶加氢脱氯制备2,3-二氯吡啶的方法，催化剂具有下列通式：αM-βN/Z，其中，M是选自Ni、Pd、Ir、Rh、Pt或其两种或更多种的混合物的金属元素，N是选自Cu、Co、Fe或其两种或三种的混合物的金属，Z是选自MgO、TiO2、活性炭、硅藻土、ZSM-5分子筛或其两种或更多种的载体；该方法具有催化剂添加量低、反应条件温和、转化率高、选择性好等特点。
CN106140193A公开了用于CFC和HCFC加氢脱氯的催化剂，催化剂前体包括主要活性成分和助剂，主要活性成分为Pd和Cu，助剂选自过渡金属、碱金属、碱土金属和稀土金属中的一种、两种或三种以上组合。作为优选的方式，助剂选自Mg、Ca、Ba、Co、Mo、Ni、Sm和Ce中的一种、两种或三种以上组合。主要活性成分和助剂负载在载体上，载体优选为活性炭、氟化铝或氧化铝。反应结果为CFC-113转化率95.35％，三氟氯乙烯选择性98.82％。
CN110013853A公开了一种气相加氢脱氯制备2,3,3,3-四氟丙烯用催化剂，催化剂由活性组分和载体组成，其中活性组分为金属Ni、Mo、W、Co、Cr、Cu、Ce、La、Mn、Fe中的一种或者多种的组合，载体为氧化物、氟化物、活性炭及分子筛中的一种，其中活性组分占催化剂总质量的0.01％～50％，该催化剂用于HCFC-244bb选择加氢脱氯反应工艺，可实现在250℃反应时，HCFC-244bb转化率达到62％，同时目标产物HFO-1234yf选择性达到63％。
US5097081公开了一种高氯化甲烷的脱氯方法，包括在氧气和催化有效量的元素周期表中的铜或贵金属的金属存在下使这种高氯化甲烷与脱氯氢气反应，所述高氯化甲烷包含四氯化碳。所述催化有效金属沉积在支撑基底上。所述支撑基底包含氧化铝或二氧化钛，其表面积为20-300m2/g，该方法避免了催化剂的结垢。
JP特许3110667B2公开了用加氢脱氯处理多氯芳族化合物的方法，在金属催化剂的存在下，通过加氢脱氯反应分解多氯芳族化合物时，使用含14个或更多碳饱和烃作为溶剂。金属催化剂是含有钯，铂，铑，钌，钴和镍中的至少一种作为金属催化剂并负载在由活性炭或氧化铝制成的载体上的金属催化剂，该方法可以有效去除环境污染物多氯代有机化合物。
脱氯反应通常为强放热反应，现有技术中脱氯催化剂存在容易失活、稳定性较差、转化率低、目标产物选择性较低等问题，仍需进行改进。
发明内容
本发明的目的是提供一种高稳定性脱氯催化剂、其制备方法和脱氯工艺。
本发明的技术方案主要为：
一种高稳定性脱氯催化剂，所述催化剂包括炭载体、炭载体表面的第一金属层，以及与第一金属层锚定结合的第二金属层，第一金属层中的第一金属选自第IB、IIB、IVB、VIB、VIIB族金属中的一种或多种，第二金属层中的第二金属选自第VIII族金属中的一种或多种，第二金属在微波反应器中与第一金属锚定结合。
第一金属层的厚度为1-5nm，第二金属层的厚度为1-2nm。
催化剂中，炭载体的质量百分含量为93-98.5％，第一金属的质量百分含量为1-5％，第二金属的质量百分含量为0.5-2％。
催化剂反应100小时后的转化率为初始转化率的92-99.9％。
优选地，催化剂反应100小时后的转化率为初始转化率的95-99.9％。
第一金属选自Cd、Zr、Cu、Ag、Mo、W、Mn、Cr、Zn、Ti、Re中的一种或多种。
第一金属优选为Cu，或者Cu与Cd、Zr、Ag、Mo、W、Mn中的一种或多种的组合。
第二金属选自Fe、Co、Ni、Rh、Pd、Ir、Pt中的一种或多种。
第二金属优选为Pd，或者Pt，或者Pd与Fe、Co、Ni、Rh、Ir、Pt中的一种或多种的组合。
本发明高稳定性脱氯催化剂的制备方法，包括在炭载体表面形成第一金属层、在第一金属层上锚定结合第二金属层的步骤。
在炭载体表面形成第一金属层的步骤具体为：将炭载体浸渍在第一金属盐溶液中，一定温度下超声混合均匀，然后干燥、焙烧，降至室温后用氧化剂液相氧化。第一金属层中的第一金属为氧化态。
氧化剂为液相氧化剂。可选地，氧化剂包括硝酸、高锰酸钾、次氯酸钠、氯酸钾、双氧水。优选地，氧化剂为双氧水。
在一种实施方式中，超声温度为60-80℃，超声时间为1-24h，超声功率为100-200W。
在一种实施方式中，干燥为以1-10℃/min的升温速率升温至120-200℃，然后恒温2-24h。
在一种实施方式中，焙烧为以5-20℃/min的升温速率由干燥温度升温至200-400℃，然后恒温0.5-6h。
本发明中，氧化剂液相氧化将炭载体表面所有的还原性基团消除，并使第一金属为氧化态。氧化剂质量分数为15-25％。氧化剂加入量以刚好全面润湿为准。
可选地，本发明第一金属盐溶液为第一金属Cd、Zr、Cu、Ag、Mo、W、Mn、Cr、Zn、Ti和/或Re的可溶性盐水溶液。
可选地，第一金属盐溶液为硝酸铜、硝酸锰、硝酸银、醋酸银、氯化铜和/或硫酸铜的水溶液。
在第一金属层上锚定结合第二金属层的步骤具体为：将液相氧化后的样品浸没于水溶液中，置于微波反应器中，于第一微波功率加热一定时间后，于第二微波功率滴入第二金属前驱体，在第一金属层上锚定结合第二金属层。
可选地，第一微波功率与第二微波功率相同或者不同。
在一种实施方式中，第一微波功率与第二微波功率相同，为0.5-2.5kW。
在一种实施方式中，第一微波功率与第二微波功率不同，第一微波功率为0.5-1.5kW，第二微波功率为1.6-2.5kW。
在一种实施方式中，第二微波功率高于第一微波功率，第一微波功率为0.5-2.5kW，第二微波功率为0.5-2.5kW。
在一种实施方式中，第一微波功率加热时间为20-300s。第一微波功率加热方式可以为连续加热。第一微波功率加热方式也可以为脉冲加热。
在一种实施方式中，第一微波功率脉冲加热方式可以为：加热2-10s后，暂停2-20s。
本发明中，第一微波功率加热时采用脉冲加热方式可以进一步增强第一金属与第二金属的锚定结合作用，增强催化剂的稳定性。
本发明通过微波反应器上的滴液漏斗滴入第二金属前驱体。于第二微波功率滴入第二金属前驱体时，保持滴加速度为匀速，滴加时间为10-60s。滴加结束后，继续于第二微波功率加热10-60s。然后，将反应物过滤、干燥即得本发明脱氯催化剂。
本发明第二微波功率加热时为连续加热。
在一种实施方式中，第一微波功率为0.5-1kW，第一微波功率加热时间为50-200s，第一微波功率加热方式为连续加热，第二微波功率为1.5-2kW，第二金属前驱体滴加时间为15-30s，滴加结束后，继续加热10-20s，第二微波功率加热方式为连续加热。
本发明第二金属前驱体包括Fe、Co、Ni、Rh、Pd、Ir和/或Pt的前驱体。
可选地，第二金属前驱体为氯铂酸溶液、钯氨络合离子溶液、硝酸铁水溶液、硝酸钴水溶液和/或硝酸镍水溶液。
在一种实施方式中，第一微波功率为1-1.5kW，第一微波功率加热时间为80-160s，第一微波功率加热方式为脉冲加热，加热2-5s后，暂停2-10s，第二微波功率为2-2.5kW，第二金属前驱体滴加时间为10-20s，滴加结束后，继续加热10-20s，第二微波功率加热方式为连续加热。
本发明方法制备的脱氯催化剂中，在微波条件下，炭载体上的第一金属作为热点，成为锚定第二金属的位点，使得第一金属与第二金属锚定结合。脱氯催化剂中第二金属包裹第一金属。本发明脱氯催化剂热稳定性高，长时间脱氯反应后仍能保持较高的转化率。
本发明脱氯催化剂适用于含氯化合物的脱氯反应。含氯化合物包括但不限于卤代乙烷、氯苯等。
本发明脱氯催化剂用于卤代乙烷脱氯时，在气相中，使卤代乙烷和还原剂的混合物与本发明高稳定性脱氯催化剂接触，反应温度为150-350℃，空速为200-500h-1。
卤代乙烷包括但不限于1,2-二氯乙烷、1,2-二氯四氟乙烷、1,1,2-三氯-1,2,2-三氟乙烷。
本发明还原剂包括液相还原剂(如甲醛、水合肼、甲酸钠等)、气相还原剂。优选地，还原剂为乙烯、乙烷或氢气。可选地，还原剂为乙烯、乙烷和氢气中的两种。
在一种实施方式中，卤代乙烷为1,2-二氯乙烷，还原剂为乙烯、乙烷或氢气。
在一种实施方式中，卤代乙烷为1,2-二氯四氟乙烷，还原剂为乙烯、乙烷或氢气。
在一种实施方式中，卤代乙烷为1,1,2-三氯-1,2,2-三氟乙烷，还原剂为乙烯、乙烷或氢气。
混合物中，卤代乙烷和还原剂的摩尔比为(1-5)：(1-5)。
可选地，卤代乙烷和还原剂的摩尔比为(2-4)：1。
本发明中，卤代乙烷的初始转化率可以达到98-100％。
本发明脱氯催化剂具有稳定性高、转化率高、选择性高等优点。
本发明高稳定性脱氯催化剂的制备方法易于工业放大生产。
本发明采用高稳定性脱氯催化剂的脱氯工艺安全环保、生产率高。
具体实施方式
下面结合具体实施例来对本发明进行进一步说明，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。
实施例1-12：脱氯催化剂的制备
将10g活性炭浸渍在第一金属盐溶液中，一定温度下超声混合均匀，然后干燥、焙烧，降至室温后滴加5滴质量分数为20％的双氧水，进行液相氧化。将液相氧化后的样品浸没于100ml水溶液中，置于微波反应器中，于第一微波功率加热一定时间后，于第二微波功率滴入第二金属前驱体。滴加结束后，继续于第二微波功率加热。然后，将反应物过滤、干燥即得脱氯催化剂。
催化剂制备参数如表1所示。
表1实施例1-12催化剂制备参数
实施例13：脱氯工艺
将实施例1-12的脱氯催化剂装入固定床反应器中，反应器内径10mm。反应产物用气相色谱进行分析。反应条件和性能如表2所示。
表2实施例1-12的催化性能
Claims (10)
1.一种高稳定性脱氯催化剂，其特征在于：所述催化剂包括炭载体、炭载体表面的第一金属层，以及与第一金属层锚定结合的第二金属层，第一金属层中的第一金属选自第IB、IIB、IVB、VIB、VIIB族金属中的一种或多种，第二金属层中的第二金属选自第VIII族金属中的一种或多种，第二金属在微波反应器中与第一金属锚定结合。
2.根据权利要求1所述的高稳定性脱氯催化剂，其特征在于：第一金属层的厚度为1-5nm，第二金属层的厚度为1-2nm。
3.根据权利要求1所述的高稳定性脱氯催化剂，其特征在于：催化剂中，炭载体的质量百分含量为93-98.5％，第一金属的质量百分含量为1-5％，第二金属的质量百分含量为0.5-2％。
4.根据权利要求1所述的高稳定性脱氯催化剂，其特征在于：催化剂反应100小时后的转化率为初始转化率的92-99.9％。
5.根据权利要求1所述的高稳定性脱氯催化剂，其特征在于：第一金属选自Cd、Zr、Cu、Ag、Mo、W、Mn、Cr、Zn、Ti、Re中的一种或多种。
6.根据权利要求1所述的高稳定性脱氯催化剂，其特征在于：第二金属选自Fe、Co、Ni、Rh、Pd、Ir、Pt中的一种或多种。
7.权利要求1所述的高稳定性脱氯催化剂的制备方法，其特征在于：包括在炭载体表面形成第一金属层、在第一金属层上锚定结合第二金属层的步骤。
8.一种脱氯工艺，其特征在于：在气相中，使卤代乙烷和还原剂的混合物与权利要求1所述的高稳定性脱氯催化剂接触，反应温度为150-350℃，空速为200-500h-1。
9.根据权利要求8所述的脱氯工艺，其特征在于：混合物中，卤代乙烷和还原剂的摩尔比为(1-5)：(1-5)。
10.根据权利要求8所述的脱氯工艺，其特征在于：卤代乙烷的初始转化率为98-100％。
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