CN110013868A - 一种选择加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂 - Google Patents
一种选择加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂 Download PDFInfo
- Publication number
- CN110013868A CN110013868A CN201910380041.0A CN201910380041A CN110013868A CN 110013868 A CN110013868 A CN 110013868A CN 201910380041 A CN201910380041 A CN 201910380041A CN 110013868 A CN110013868 A CN 110013868A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tetrafluoropropene
- tungsten
- dechlorination
- tungsten phosphide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 17
- -1 2,3,3,3- tetrafluoropropene tungsten Chemical compound 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical class FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 17
- 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 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 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 4
- JRHNUZCXXOTJCA-UHFFFAOYSA-N 1-fluoropropane Chemical compound CCCF JRHNUZCXXOTJCA-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGYLHZMNVGBXDQ-UHFFFAOYSA-N 1,1-dichloro-2,3,3,3-tetrafluoroprop-1-ene Chemical class ClC(Cl)=C(F)C(F)(F)F QGYLHZMNVGBXDQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003657 tungsten Chemical class 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 group ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开一种一种选择加氢脱氯制备2,3,3,3‑四氟丙烯用磷化钨催化剂。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组成为体相WP或WP/载体,其中WP为金属钨与非金属元素磷结合而成具有晶体结构的磷化钨共价化合物。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 2017,9,824–832)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。
CN102958879.A公布了一种2,3,3,3-四氟丙烯的制造方法,它是一种由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在氢气存在条件下发生脱氯化氢反应制造2,3,3,3-四氟丙烯。CN108178719.A、CN102947255.A和CN102947254.A同样公开了2,3,3,3-四氟丙烯的制造方法,反应原料也是1,1-二氯-2,3,3,3-四氟丙烯或1-氯-2,3,3,3-四氟丙烯和氢气。但这几篇专利公开的制备方法中,1,1-二氯-2,3,3,3-四氟丙烯或1-氯-2,3,3,3-四氟丙烯虽然可以与氢气直接一步反应制备2,3,3,3-四氟丙烯,但是在实际反应过程中,原料化合物中的双键会优先与氢气反应生成饱和氟氯烷烃,从而导致目标产物选择性降低。同时,使用的催化剂活性组分都为贵金属,反应原料也需要经过繁杂步骤制备,导致整个反应工艺的成本增加。
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,磷化钨作为活性组分,通过浸渍或者共沉淀的方法制备所需催化剂。
本发明所述加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂组成为体相WP或WP/载体,其中WP为金属钨与非金属元素磷结合而成具有晶体结构的磷化钨共价化合物,载体选择氧化物、氟化物及活性炭、分子筛的固体载体,磷化钨占催化剂总质量的0.01%~50%。
所述载体的比表面积为10~2000m2/g。
本发明所述加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂,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。
本发明所述加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂的制备方法包括以下步骤:
(1)按照W/P摩尔比为1/1将含钨盐的水溶液与含磷盐的水溶液混合,制备过渡金属磷酸盐,调节pH值为1~3,得到透明溶液;
所述含钨盐选用钨酸铵、偏钨酸铵的一种;所述含磷盐选用磷酸氢二铵、磷酸氢二钠、磷酸二氢铵、磷酸二氢钠、次磷酸铵、次磷酸钠、亚磷酸铵、亚磷酸钠的一种;
(2)通过分步或共浸渍的方法,将过渡金属磷酸盐溶液负载到载体上,载体质量根据负载量0.01%~50%的变化而改变,固体样品常温老化8~12h,随后在90~120℃烘干水分,最后在400-550℃进行焙烧处理得到负载型磷化钨催化剂前体盐;
(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550~650℃,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,含原料成本低、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280℃反应时,HCFC-244bb转化率达到63%,同时目标产物HFO-1234yf选择性达到86%。
附图说明
图1是负载型WP催化剂XRD谱图。
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280℃后通入HCFC-244bb和氢气,接触时间为8s,H2压力0.2MPa,H2/HCFC-244bb摩尔比为2/1。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:制备WP/氧化物(氟化物或分子筛)催化剂
室温下将3.73g偏钨酸铵((NH4)6W12H2O40·nH2O)和1.87g磷酸氢二铵((NH4)2HPO4)添加到20mL去离子水溶液中,然后用浓硝酸调节溶液pH至2-3,得到澄清溶液。分别按照负载量为0.5%、5%、10%、20%、30%将上述溶液浸渍到一定质量氧化物、氟化物或分子筛上,之后室温老化12h,在120℃干燥12h烘干水分,并且在500℃焙烧6h,获得负载型WP的氧化物前驱体。采用原位程序升温还原的方法制备磷化物催化剂。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℃,然后从400℃以1℃/min升温到650℃,并在还原终温下保持2h。
实施例2:制备WP/活性炭催化剂
室温下将3.73g偏钨酸铵((NH4)6W12H2O40·nH2O)和1.87g磷酸氢二铵((NH4)2HPO4)添加到20mL去离子水溶液中,然后用浓硝酸调节溶液pH至2-3,得到澄清溶液。分别按照负载量为5%、10%、20%、30%将上述溶液浸渍到一定质量活性碳上,之后室温老化12h,在120℃干燥12h烘干水分,并且在氮气气氛500℃焙烧3h,获得活性炭担载WP的氧化物前驱体。采用原位程序升温还原的方法制备磷化物催化剂。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℃,然后从400℃以1℃/min升温到650℃,并在还原终温下保持2h。
实施例3:采用实施例1和2中方法制备的催化剂,将其应用到HCFC-244bb气相选择加氢脱氯制备HFO-1234yf的反应中去,运行8h后,反应结果如下表:
表1不同载体担载不同负载量的WP催化剂上HCFC-244bb进行选择加氢脱氯反应时转化率和产物选择性
编号 | 催化剂 | HCFC-244bb转化率/% | HFO-1234yf选择性/% |
1 | 0.5wt.%WP/SiO<sub>2</sub> | 20.1 | 50.2 |
2 | 5wt.%WP/SiO<sub>2</sub> | 28.9 | 60.1 |
3 | 10wt.%WP/SiO<sub>2</sub> | 33.5 | 70.1 |
4 | 20wt.%WP/SiO<sub>2</sub> | 36.8 | 83.2 |
5 | 30wt.%WP/SiO<sub>2</sub> | 40.2 | 85.1 |
6 | 10wt.%WP/TiO<sub>2</sub> | 26.1 | 55.2 |
7 | 30wt.%WP/TiO<sub>2</sub> | 32.1 | 61.0 |
8 | 30wt.%WP/MgF<sub>2</sub> | 38.9 | 65.1 |
9 | 30wt.%WP/ZSM-5 | 41.9 | 74.3 |
10 | 30wt.%WP/MCM-41 | 42.6 | 76.9 |
11 | 5wt.%WP/活性炭 | 45.2 | 70.2 |
12 | 10wt.%P/活性炭 | 50.5 | 75.1 |
13 | 20wt.%WP/活性炭 | 60.1 | 83.1 |
14 | 30wt.%WP/活性炭 | 62.7 | 86.2 |
Claims (3)
1.一种加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂,其特征在于所述催化剂组成为体相WP或WP/载体,其中WP为金属钨与非金属元素磷结合而成具有晶体结构的磷化钨共价化合物,载体为氧化物、氟化物、活性炭及分子筛中的一种,其中磷化钨占催化剂总质量的0.01%~50%。
2.根据权利要求1所述一种加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂,其特征在于所述载体的比表面积为10~2000m2/g。
3.根据权利要求1所述一种加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂,其特征在于用于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。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910380041.0A CN110013868B (zh) | 2019-05-08 | 2019-05-08 | 一种选择加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910380041.0A CN110013868B (zh) | 2019-05-08 | 2019-05-08 | 一种选择加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110013868A true CN110013868A (zh) | 2019-07-16 |
CN110013868B CN110013868B (zh) | 2021-10-01 |
Family
ID=67193290
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910380041.0A Active CN110013868B (zh) | 2019-05-08 | 2019-05-08 | 一种选择加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110013868B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110499529A (zh) * | 2019-08-28 | 2019-11-26 | 四川大学 | 一种常规超导体材料磷化钨(wp)的高温高压制备 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102921441A (zh) * | 2012-10-30 | 2013-02-13 | 陕西高新能源发展有限公司 | 磷化钨催化剂的制备方法 |
CN102935374A (zh) * | 2012-10-30 | 2013-02-20 | 陕西高新能源发展有限公司 | 磷化钨催化剂的制备方法 |
CN103721368A (zh) * | 2014-01-02 | 2014-04-16 | 东南大学 | 一种三氯乙烯加氢脱氯的方法 |
CN105344368A (zh) * | 2015-09-28 | 2016-02-24 | 东南大学 | 一种用于加氢脱氯反应的过渡金属磷化物的制备方法及应用 |
CN108367285A (zh) * | 2015-12-14 | 2018-08-03 | 阿科玛法国公司 | 用铬催化剂进行气相催化氟化 |
CN108727158A (zh) * | 2018-05-22 | 2018-11-02 | 杨彩花 | 一种催化乙酸加氢制乙醇的方法 |
-
2019
- 2019-05-08 CN CN201910380041.0A patent/CN110013868B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102921441A (zh) * | 2012-10-30 | 2013-02-13 | 陕西高新能源发展有限公司 | 磷化钨催化剂的制备方法 |
CN102935374A (zh) * | 2012-10-30 | 2013-02-20 | 陕西高新能源发展有限公司 | 磷化钨催化剂的制备方法 |
CN103721368A (zh) * | 2014-01-02 | 2014-04-16 | 东南大学 | 一种三氯乙烯加氢脱氯的方法 |
CN105344368A (zh) * | 2015-09-28 | 2016-02-24 | 东南大学 | 一种用于加氢脱氯反应的过渡金属磷化物的制备方法及应用 |
CN108367285A (zh) * | 2015-12-14 | 2018-08-03 | 阿科玛法国公司 | 用铬催化剂进行气相催化氟化 |
CN108727158A (zh) * | 2018-05-22 | 2018-11-02 | 杨彩花 | 一种催化乙酸加氢制乙醇的方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110499529A (zh) * | 2019-08-28 | 2019-11-26 | 四川大学 | 一种常规超导体材料磷化钨(wp)的高温高压制备 |
CN110499529B (zh) * | 2019-08-28 | 2022-01-04 | 四川大学 | 一种常规超导体材料磷化钨(wp)的高温高压制备 |
Also Published As
Publication number | Publication date |
---|---|
CN110013868B (zh) | 2021-10-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2495042B1 (en) | PREPARATION AND APPLICATION of a TUNGSTEN CARBIDE CATALYST SUPPORTED ON MESOPOROUS CARBON | |
JP2013505119A (ja) | グリセリンの脱水反応によってアクロレインおよび/またはアクリル酸を製造するための触媒および方法 | |
WO2010060345A1 (zh) | 一种多羟基化合物制乙二醇的方法 | |
Liu et al. | Kinetic insight into the effect of the catalytic functions on selective conversion of cellulose to polyols on carbon-supported WO3 and Ru catalysts | |
CN103769148A (zh) | 丙烯醛氧化制备丙烯酸催化剂、制备方法及其用途 | |
CN103521234A (zh) | 由丙烯醛氧化制备丙烯酸的催化剂及其制备方法 | |
CN109967101A (zh) | 一种选择加氢脱氯制备三氟氯乙烯用催化剂 | |
MX2009010709A (es) | Catalizadores de oxido de metal mixto mejorados y procedimientos para (am) oxidacion de hidrocarburos de alcano inferior. | |
KR20140004733A (ko) | 탄소상 니켈을 포함하는 수소화 촉매 | |
CN104874406A (zh) | 一种氢解催化剂及其制备方法 | |
CN108079988A (zh) | C5、c6烷烃异构化的催化剂及制备和应用 | |
KR20180081659A (ko) | 탈수소 촉매 및 그의 제조방법 | |
CN110013868A (zh) | 一种选择加氢脱氯制备2,3,3,3-四氟丙烯用磷化钨催化剂 | |
KR102162079B1 (ko) | 촉매 담체의 제조방법 및 탈수소 촉매 | |
CN109967103A (zh) | 一种气相选择加氢脱氯制备2,3,3,3-四氟丙烯用磷化钼催化剂 | |
CN106807360A (zh) | 一种抗硫脱硝催化剂的制备方法 | |
JP2013040179A (ja) | グリセリンの脱水反応によってアクロレインおよび/またはアクリル酸を製造するための触媒および方法 | |
CN110013867A (zh) | 一种气相选择加氢脱氯制备2,3,3,3-四氟丙烯用磷化镍催化剂 | |
CN1363544A (zh) | 浸渍法制备3-羟基丙醛加氢催化剂 | |
CN103521235A (zh) | 由丙烯醛氧化制备丙烯酸催化剂及其制备方法 | |
CN102847557B (zh) | 一种y型沸石固载磷钨酸的瓶中船型催化剂及其制备方法 | |
CN109999864A (zh) | 一种选择加氢脱氯制备2,3,3,3-四氟丙烯用催化剂 | |
CN111686726A (zh) | 新型碳基贵金属催化剂的制备方法及应用 | |
CN115608353B (zh) | 用于合成烷基硫醇的催化剂及其制备方法、烷基硫醇的制备方法 | |
CN102731275B (zh) | 用于通过甘油脱水反应制备丙烯醛和/或丙烯酸的催化剂和方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |