CN110013853B - 一种气相加氢脱氯制备2,3,3,3-四氟丙烯用催化剂 - Google Patents
一种气相加氢脱氯制备2,3,3,3-四氟丙烯用催化剂 Download PDFInfo
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- CN110013853B CN110013853B CN201910380027.0A CN201910380027A CN110013853B CN 110013853 B CN110013853 B CN 110013853B CN 201910380027 A CN201910380027 A CN 201910380027A CN 110013853 B CN110013853 B CN 110013853B
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- catalyst
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- tetrafluoropropene
- gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006298 dechlorination reaction Methods 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims 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 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 abstract 1
- 230000002779 inactivation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000011068 loading method Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000002791 soaking Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000010949 copper Substances 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 238000005470 impregnation 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
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical compound ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 description 1
- QGYLHZMNVGBXDQ-UHFFFAOYSA-N 1,1-dichloro-2,3,3,3-tetrafluoroprop-1-ene Chemical compound ClC(Cl)=C(F)C(F)(F)F QGYLHZMNVGBXDQ-UHFFFAOYSA-N 0.000 description 1
- GDPWRLVSJWKGPJ-UHFFFAOYSA-N 1-chloro-2,3,3,3-tetrafluoroprop-1-ene Chemical compound ClC=C(F)C(F)(F)F GDPWRLVSJWKGPJ-UHFFFAOYSA-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
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910017315 Mo—Cu Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B01J37/16—Reducing
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明公开一种一种气相加氢脱氯制备2,3,3,3‑四氟丙烯用催化剂。是为了解决传统氟氯烃加氢脱氯催化剂成本高，易失活的难题。本发明公开的催化剂其特征在于所述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。本发明中的催化剂性能优异，活性高，稳定性好，且反应温度低，有效降低反应能耗，具有工业化应用价值。
Description
技术领域
本发明涉及一种催化剂，具体涉及一种制备2,3,3,3-四氟丙烯用催化剂。属于多项催化技术领域。
背景技术
2,3,3,3-四氟丙烯，简称HFO-1234yf，分子式为CF3CF＝CH2，无毒、不燃，ODP为零，GWP约为4，被认为是HFC-134a的理想替代品，是最有潜力的第四代低碳制冷剂之一。
迄今，在已知的众多HFO-1234yf合成方法中，主要是以1,1,2,3-四氯丙烯和无水氟化氢为原料经三步合成生成目标产物(中国专利CN102603465.A)，反应的最后一步是通过2-氯-1,1,1,2-四氟丙烷(HCFC-244bb)在催化剂存在条件下发生脱氯化氢反应。文献(ChemCatChem 2017,9,824)和专利(US8058486B2)报道这步反应往往需要较高的反应温度，这不仅能耗高还容易导致积碳使催化剂快速失活反应，工业应用价值低。
中国专利CN108178719.A、CN102947255.A、CN102947254.A公开了1,1-二氯-2,3,3,3-四氟丙烯或1-氯-2,3,3,3-四氟丙烯为原料化合物采用加氢脱氯的工艺制备HFO-1234yf，但所用催化剂活性组分都为贵金属钯，原料不易得，同时催化剂价格昂贵，导致生产成本升高。
Phys.Chem.Chem.Phys.,1999,1,2367和J.Mol.Catal.A:Chem.2000,155,111以及Appl.Catal.A:Gen.2000,194,55报道CCl2F2在AlPO4催化剂上的直接分解脱氯反应性能，所需反应温度大于350℃。
目前通过选择加氢脱氯制备HFO-1234yf的工艺存在原材料不易得，催化剂价格昂贵的问题。基于此，为应对日益严峻的环保形势和工业应用，迫切需要设计、制备低温高活性、环保催化剂用于HCFC-244bb气相选择加氢脱氯制备HFO-1234yf。
发明内容
本发明要解决的技术问题是针对现有技术存在的缺陷与不足，提供一种非贵金属、环境友好、低温活性高的气相选择加氢脱氯反应用于制备HFO-1234yf的催化剂。
为了实现本发明的目的，得到一种非贵金属、环境友好、低温活性高的催化剂，设想使用具有高比表面积固体材料作为活性载体，单金属或多金属作为活性组分，通过浸渍或者共沉淀的方法制备所需催化剂。
本发明所述所述一种气相加氢脱氯制备2,3,3,3-四氟丙烯用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％。
所述载体的比表面积为10～2000m2/g。
本发明所述所述一种气相加氢脱氯制备2,3,3,3-四氟丙烯用催化剂，用于2-氯-1,1,1,2-四氟丙烷气相选择加氢脱氯制备2,3,3,3-四氟丙烯，反应温度为100～300℃，反应压力为0.1～2.0MPa，原料空速20～200h-1，原料氢气与2-氯-1,1,1,2-四氟丙烷的摩尔比为1/1～5/1。
本发明所述所述一种气相加氢脱氯制备2,3,3,3-四氟丙烯用催化剂的制备方法包括以下步骤：
(1)根据负载量将不同质量的金属盐的水溶液通过分步或共浸渍的方法负载到载体上，所得固体样品常温老化8～12h，随后在90～120℃烘干水分，最后在350～550℃进行焙烧处理得到催化剂前体盐；
所述金属盐选用硝酸镍、氯化镍、醋酸镍、钼酸铵、钨酸铵、偏钨酸铵、硝酸钴、氯化钴、氢氧化钴、氯化铬、硝酸铬、氯化铜、硝酸铜、硝酸铈、硝酸镧、硝酸锰、氯化锰、硝酸铁、氯化铁、硝酸亚铁、氯化亚铁的一种；
(3)在氢气气氛下通过程序升温方式对催化剂前驱体进行还原处理，所述还原条件包括：压力0.2～1.2MPa，H2流量80～120mL/min，温度350～450℃，时间2～5h，最终得到催化剂。
本发明的有益效果：本发明与现有技术相比，具有如下有益的技术效果：
①本发明提供了一种不使用贵金属元素，原料成本低、绿色环保、高温抗烧结能力好催化剂；②对比文献和专利报道对于HCFC-244bb脱氯化氢所需高于350℃的高温条件，本发明提供的催化剂用于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％。并且寿命长，可稳定运行200h。
具体实施方式
下面给出本发明的具体实施例，但并不限制本发明的范围。
本发明所述加氢脱氯制备HFO-1234yf用催化剂性能评价：
量取5mL催化剂转入固定床管式反应器中，催化剂床层温度到达250℃后通入HCFC-244bb和氢气，接触时间为4s，H2压力0.2MPa，H2/HCFC-244bb摩尔比为3。运行8h后产物经水、碱洗吸收氟化氢、氯化氢后进气相色谱仪进行分析，采用面积归一化法计算HCFC-244bb的转化率及目标产物HFO-1234yf选择性。
实施例1
按照Ni的负载量为20％，称取9.48g硝酸镍加到去离子水溶液中，得到澄清溶液。将上述溶液等体积浸渍到9.6g二氧化硅上，之后室温老化12h，在120℃干燥12h烘干水分，并且在500℃焙烧4h，获得Ni/SiO2的氧化物前驱体。采用原位程序升温还原的方法制备催化剂。程序升温步骤主要包括两步：(1)在H2气氛下(流速150mL/min)从室温以5℃/min升温至120℃，并且在120℃下保持1h以驱除催化剂吸附的水；(2)从120℃以5℃/min的升温速率升至400℃，并在此温度下下保持2h，制成催化剂。通过评价，HCFC-244bb的转化率为30.1％，HFO-1234yf选择性为50％。
实施例2
按照Ni的负载量为20％，称取9.48g硝酸镍加到去离子水溶液中，得到澄清溶液。将上述溶液等体积浸渍到9.6g的活性炭上，之后室温老化12h，在120℃干燥12h烘干水分，并且在N2气氛下500℃焙烧4h，获得Ni/C的氧化物前驱体。采用原位程序升温还原的方法制备催化剂。程序升温步骤主要包括两步：(1)在H2气氛下(流速150mL/min)从室温以5℃/min升温至120℃，并且在120℃下保持1h以驱除催化剂吸附的水；(2)从120℃以5℃/min的升温速率升至400℃，并在此温度下下保持2h，制成催化剂。通过评价，HCFC-244bb的转化率为48.9％，HFO-1234yf选择性达到64％。
实施例3
按照Ni的负载量为10％，称取9.48g硝酸镍加到去离子水溶液中，得到澄清溶液。将上述溶液等体积浸渍到21.9g氟化镁上，之后室温老化12h，在120℃干燥12h烘干水分，并且在400℃焙烧4h，获得Ni/MgF2的氧化物前驱体。采用原位程序升温还原的方法制备催化剂。程序升温步骤主要包括两步：(1)在H2气氛下(流速150mL/min)从室温以5℃/min升温至120℃，并且在120℃下保持1h以驱除催化剂吸附的水；(2)从120℃以5℃/min的升温速率升至400℃，并在此温度下下保持2h，制成催化剂。通过评价，HCFC-244bb的转化率为35.1％，HFO-1234yf选择性达到38％。
实施例4
按照Ni的负载量为10％，称取9.48g硝酸镍加到去离子水溶液中，得到澄清溶液。将上述溶液等体积浸渍到21.9g氟化铝上，之后室温老化12h，在120℃干燥12h烘干水分，并且在400℃焙烧4h，获得Ni/AlF3的氧化物前驱体。采用原位程序升温还原的方法制备催化剂。程序升温步骤主要包括两步：(1)在H2气氛下(流速150mL/min)从室温以5℃/min升温至120℃，并且在120℃下保持1h以驱除催化剂吸附的水；(2)从120℃以5℃/min的升温速率升至400℃，并在此温度下下保持2h，制成催化剂。通过评价，HCFC-244bb的转化率为38.7％，HFO-1234yf选择性达到38％。
实施例5
按照Mo的负载量为20％，称取3.52g钼酸铵加到去离子水溶液中，得到澄清溶液。将上述溶液等体积浸渍到7.65g活性炭上，之后室温老化12h，在120℃干燥12h烘干水分，并且在N2气氛下500℃焙烧4h，获得Mo/C的氧化物前驱体。采用原位程序升温还原的方法制备催化剂。程序升温步骤主要包括两步：(1)在H2气氛下(流速150mL/min)从室温以5℃/min升温至120℃，并且在120℃下保持1h以驱除催化剂吸附的水；(2)从120℃以5℃/min的升温速率升至400℃，并在此温度下下保持2h，制成催化剂。通过评价，HCFC-244bb的转化率为45.7％，HFO-1234yf选择性达到51％。
实施例6
按照Ni的负载量为10％，Mo的负载量为10％，称取9.8g硝酸镍和4.6g钼酸铵加到去离子水溶液中，得到澄清溶液。将上述溶液等体积浸渍到20g活性炭上，之后室温老化12h，在120℃干燥12h烘干水分，并且在N2气氛下500℃焙烧4h，获得Ni-Mo/C的氧化物前驱体。采用原位程序升温还原的方法制备催化剂。程序升温步骤主要包括两步：(1)在H2气氛下(流速150mL/min)从室温以5℃/min升温至120℃，并且在120℃下保持1h以驱除催化剂吸附的水；(2)从120℃以5℃/min的升温速率升至400℃，并在此温度下下保持2h，制成催化剂。通过评价，HCFC-244bb的转化率为51.7％，HFO-1234yf选择性达到59％。
实施例7
按照Ni的负载量为10％，Cu的负载量为20％，称取9.8g硝酸镍和9.5g硝酸铜加到去离子水溶液中，得到澄清溶液。将上述溶液等体积浸渍到20g活性炭上，之后室温老化12h，在120℃干燥12h烘干水分，并且在N2气氛下500℃焙烧4h，获得Ni-Cu/C的氧化物前驱体。采用原位程序升温还原的方法制备催化剂。程序升温步骤主要包括两步：(1)在H2气氛下(流速150mL/min)从室温以5℃/min升温至120℃，并且在120℃下保持1h以驱除催化剂吸附的水；(2)从120℃以5℃/min的升温速率升至400℃，并在此温度下下保持2h，制成催化剂。通过评价，HCFC-244bb的转化率为45.7％，HFO-1234yf选择性达到70％。
实施例8
按照Ni的负载量为10％，Mo的负载量为10％，Cu的负载量为5％，称取7.78g硝酸镍、3.68g钼酸铵和3.80g硝酸铜加到去离子水溶液中，得到澄清溶液。将上述溶液等体积浸渍到15g活性炭上，之后室温老化12h，在120℃干燥12h烘干水分，并且在N2气氛下500℃焙烧4h，获得Ni-Mo-Cu/C的氧化物前驱体。采用原位程序升温还原的方法制备催化剂。程序升温步骤主要包括两步：(1)在H2气氛下(流速150mL/min)从室温以5℃/min升温至120℃，并且在120℃下保持1h以驱除催化剂吸附的水；(2)从120℃以5℃/min的升温速率升至400℃，并在此温度下下保持2h，制成催化剂。通过评价，HCFC-244bb的转化率为62％，HFO-1234yf选择性达到63％。
实施例9
按照W的负载量为10％，称取3.73g偏钨酸铵加到去离子水溶液中，得到澄清溶液。将上述溶液等体积浸渍到10.4g活性炭上，之后室温老化12h，在120℃干燥12h烘干水分，并且在N2气氛下500℃焙烧4h，获得W/C的氧化物前驱体。采用原位程序升温还原的方法制备催化剂。程序升温步骤主要包括两步：(1)在H2气氛下(流速150mL/min)从室温以5℃/min升温至120℃，并且在120℃下保持1h以驱除催化剂吸附的水；(2)从120℃以5℃/min的升温速率升至400℃，并在此温度下下保持2h，制成催化剂。通过评价，HCFC-244bb的转化率为25.7％，HFO-1234yf选择性达到36％。
实施例10
本发明的HCFC-244bb加氢脱氯制备HFO-1234yf用催化剂寿命试验
对实施例8制备的催化剂进行寿命试验，催化剂装填量5mL，反应温度为250℃，H2与HCFC-244bb摩尔比为3，接触时间为4s，反应持续运行200h，反应产物经水洗、碱洗吸收HCl后通过气相色谱进行分析，评价结果见表1。
表1寿命试验
Claims (1)
1.一种催化剂用于2-氯-1,1,1,2-四氟丙烷气相选择加氢脱氯制备2,3,3,3-四氟丙烯的方法，其特征在于，所述催化剂前驱体是在氢气气氛下通过程序升温方式进行还原处理，还原条件为：压力0.2-1.2 MPa，氢气流量为80-120 mL min-1，温度为350-450 oC，时间2-5h；
所述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%；载体的比表面积为10~2000 m2/g；
所述催化剂用于2-氯-1,1,1,2-四氟丙烷气相选择加氢脱氯制备2,3,3,3-四氟丙烯，反应温度为100~300 oC，反应压力为0.1~2.0 MPa，原料空速20~200 h-1，原料氢气与2-氯-1,1,1,2-四氟丙烷的摩尔比为1/1~5/1。
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| US11833489B2 (en) | 2023-12-05 |
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