CN116943749A - 一种氨水预处理活性炭负载三元金属催化剂及其应用 - Google Patents
一种氨水预处理活性炭负载三元金属催化剂及其应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 235000011114 ammonium hydroxide Nutrition 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 14
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 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 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 5
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- -1 molybdenum modified skeletal nickel catalyst Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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Abstract
本发明公开了一种氨水预处理活性炭负载三元金属催化剂及其应用,以经氨水预处理的活性炭为载体,其上负载有贵金属元素、过渡金属元素和助剂碱土金属元素。其中,贵金属元素选自W、Re和Ru,过渡金属元素选自Nb、In和Pb,助剂碱土金属元素选自Ba、Ca和Sr。本发明应用于环戊酮催化加氢制环戊醇,在环戊酮转化率达100%的同时,产物环戊醇的选择性可达100%,可极大减轻产物的分离提纯负担,降低生产成本;催化反应过程操作温度低且不使用溶剂,过程绿色低能耗;催化剂呈现高活性,反应时间较短,可提高生产效率。
Description
技术领域
本发明属于工业催化剂技术领域,具体涉及一种氨水预处理活性炭负载三元金属催化剂及其应用。
背景技术
环戊醇是一种重要的化工原料,主要用作香料及药品的溶剂和染料中间体。环戊醇可以由环戊酮加氢制得。
现有技术中,CN114931938B公开了使用碳纳米管外壁负载铂纳米粒子催化剂用于环戊酮加氢制环戊醇,在160℃反应温度,2MPa氢气压力,使用异丙醇为溶剂,反应6h后环戊酮转化率可达90%,环戊醇选择性达到91%。除此之外,曾有专利文献公开了酮类化合物加氢制醇类化合物的催化剂及工艺。专利CN1152744C,CN1114490C和CN1347758A中公开了仲辛酮加氢制备仲辛醇的方法,使用其自制的催化剂体系(含铜催化剂,含镍催化剂),采用固定床液相加氢工艺来实现,反应温度为100-250℃。仲辛醇的选择性为96%-99.5%。CN1974514A公开了2-辛酮加氢还原制2-辛醇的方法,在磁稳定床反应器中加入具有铁磁性的加氢催化剂,在温度70-120℃,压力0.3-2.5MPa,液体体积空速为1-50h-1,氢气与含2-辛酮的溶液体积比为2-100:1,磁场强度10-50kA/m的条件下反应,2-辛醇可以达到70%的收率。专利CN1083415C采用压片成型的CuO-ZnO混合物为催化剂,在反应温度150-250℃的条件下丙酮气相加氢制异丙醇的转化率和选择性达到99%。日本专利平2-279643公开了的Ru/Al2O3催化丙酮加氢的工艺苛刻,反应压力在9MPa,设备的投资较大。日本专利平-41038,苏联专利SU1118632A介绍了采用Cu-Cr催化剂的丙酮加氢方法,俄罗斯专利RU2047590使用了含有NiO,CuO等成分的催化剂,但这些催化剂的转化率不高,且选择性较差,Cr2O3作为助剂的使用的同时会造成环境的污染,不符合绿色化工的要求。CN103030525A公开了一种丙酮液相加氢制备异丙醇的方法,但反应温度较高,在100-200℃,丙酮的转化率为96%以上,异丙醇的选择性大于95%。CN1962588公开了以镍钴双金属负载到活性炭的催化剂用于丙酮的气相加氢连续式反应,反应温度在100-150℃,压力在1.0-1.5MPa,可获得较高的丙酮转化率和异丙醇选择性。CN103706365公开了镍铜双金属负载型催化剂用于丙酮常压气相固定床加氢,反应温度在100-150℃,异丙醇选择性达100%,丙酮的转化率可达85.5%以上。CN103706377A,CN103752327A公开了以Pt,Fe,Sn,Co为主要成分的金属催化剂的丙酮液相加氢制备异丙醇,反应温度在100-150℃,反应时间为4h。USP4,182,721公开了一种将钼改性的骨架镍催化剂用于酮类化合物的催化加氢,虽然反应的条件比较温和(60℃,2.1MPa),但是产物选择性较差。USP4,459,419公开了一种有机酮或醛加氢的方法,使用的催化剂为负载到分子筛上的钌催化剂,并列举了糠醇加氢制四氢糠醇的应用,但该反应体系所需的压力较高,达12.7MPa。
现有技术中公开的酮类化合物加氢过程的操作温度较高,或操作条件对设备要求较高,或转化率和产物的选择性无法同时达到高标准。因此,如果开发出一种可在较低操作温度下反应,不使用溶剂,并表现出高活性和高产物选择性的多相催化剂可减轻产物分离提纯环节的负担,降低能耗,极大降低生产过程成本。低能耗且高效地进行生产符合绿色化工的生产要求。
发明内容
本发明目的在于克服现有技术缺陷,提供一种氨水预处理活性炭负载三元金属催化剂。
本发明的另一目的在于提供上述氨水预处理活性炭负载三元金属催化剂的应用。
本发明的技术方案如下:
一种氨水预处理活性炭负载三元金属催化剂,其特征在于:以经氨水预处理的活性炭为载体,其上负载有贵金属元素、过渡金属元素和助剂碱土金属元素,其中,贵金属元素选自W、Re和Ru,过渡金属元素选自Nb、In和Pb,助剂碱土金属元素选自Ba、Ca和Sr;
上述氨水预处理包括:使用氨水溶液与活性炭进行混合搅拌并加热,氨水溶液浓度为5%-15%,处理温度为50-100℃,处理时间为1-6h,降至室温后使用去离子水过滤并洗涤至中性,80℃真空干燥12h后在氩气气氛下200-400℃焙烧1-3h。
在本发明的一个优选实施方案中,所述氩气气氛中的氩气的流量为20-50mL/min。
进一步优选的,所述焙烧的升温速率为2-10℃/min。
在本发明的一个优选实施方案中,所述贵金属元素的负载量为0.1-1.5wt.%,所述过渡金属元素的负载量为0.5-2.5wt.%,所述助剂碱土金属元素的负载量为0.2-1.5wt.%。
上述氨水预处理活性炭负载三元金属催化剂在环戊酮加氢制环戊醇中的应用。
在本发明的一个优选实施方案中,采用间歇式高压釜液相加氢过程,不使用溶剂。
进一步优选的,所述间歇式高压釜液相加氢过程中,氢气压力为0.5-5.5MPa,反应操作温度为室温20-40℃,催化剂投料量/底物为0.001-0.01g/mL,反应时间为0.5-2h。
一种环戊酮加氢制环戊醇的方法,采用上述氨水预处理活性炭负载三元金属催化剂。
在本发明的一个优选实施方案中,采用间歇式高压釜液相加氢过程,不使用溶剂。
进一步优选的,所述间歇式高压釜液相加氢过程中,氢气压力为0.5-5.5MPa,反应操作温度为室温20-40℃,催化剂投料量/底物为0.001-0.01g/mL,反应时间为0.5-2h。
本发明的有益效果是:
1、本发明的氨水预处理活性炭负载三元金属催化剂的液相加氢过程操作温度为室温20-40℃,操作温度较低,能耗较低。操作压力适中,设备投资不大。
2、本发明的催化反应过程不使用溶剂,过程绿色。催化剂呈现高活性,反应时间较短,可提高生产效率。
3、本发明在环戊酮转化率达100%的同时,环戊醇的产物选择性可达100%,可极大减轻产物的分离提纯负担,降低生产成本。
4、本发明的催化剂制备和生产方法相对简单易行,适合大批量生产使用。
具体实施方式
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。
实施例1
采用100mL 5%的氨水溶液与1g活性炭混合,60℃加热下持续搅拌3h。降至室温后过滤洗涤至中性,80℃真空干燥12h。将干燥后的活性炭在氩气气氛下300℃焙烧3h,氩气流量为20mL/min,升温速率为5℃/min,获得经氨水处理的活性炭。
称取0.015g的硝酸钡,0.015g的硝酸铅和0.8g PVP,放入50mL去离子水中,搅拌30min后用氢氧化钠调节pH=10,加入0.6g的上述经氨水预处理的活性炭与6mL水合肼,水合肼的滴加速度为10滴/min,持续搅拌3h后过滤洗涤至中性,接着经80℃真空干燥12h后,在氢气中以5℃/min升温至500℃,氢气流量为60mL/min,恒温3h后降至室温,制得Pb-Ba/C。
称取0.012g的高铼酸铵放入50mL去离子水中,搅拌30min。将上述Pb-Ba/C放入上述溶液中,持续搅拌2h后用氨水调节pH=10,在冰水浴的条件下滴加3mL水合肼,水合肼的滴加速度为10滴/min,持续搅拌2h后过滤洗涤至中性,在80℃真空干燥12h。将干燥后的催化剂在氢气气氛下以2℃/min升至300℃,恒温2h后降至室温,氢气流量为80mL/min,制得所述氨水预处理活性炭负载三元金属催化剂。
采用本实施例中所制得的催化剂用于环戊酮加氢反应:催化剂投料量/底物为0.01g/mL,在间歇式高压反应釜中反应,反应温度25℃,反应时间为1.5h,氢气压力为5.0MPa,搅拌速率为500rpm。测得环戊酮加氢的转化率为100%,环戊醇的选择性达100%。
实施例2
该实施例凸显氨水处理这一步骤在产物选择性调控方面所起到的关键作用,即对催化剂载体活性炭不进行氨水处理,直接用于制备催化剂,其余同实施例1,制得所述未氨水预处理活性炭负载三元金属催化剂。
采用本实施例中所制得的催化剂用于环戊酮加氢反应:催化剂投料量/底物为0.01g/mL,在间歇式高压反应釜中反应,反应温度25℃,反应时间为2h,氢气压力为5.0MPa,搅拌速率为500rpm。测得环戊酮加氢的转化率为85.9%,环戊醇的选择性为97.2%。
实施例3
该实施例凸显氨水处理条件的变化对催化活性的影响,即改变实施例1中所用活性炭的氨水处理条件,采用100mL 15%的氨水溶液与1g活性炭混合,100℃加热下持续搅拌3h。降至室温后过滤洗涤至中性,80℃真空干燥12h。将干燥后的活性炭在氩气气氛下300℃焙烧3h,氩气流量为20mL/min,升温速率为5℃/min,其余同实施例1,制得所述氨水预处理活性炭负载三元金属催化剂。
采用本实施例中所制得的催化剂用于环戊酮加氢反应:催化剂投料量/底物为0.01g/mL,在间歇式高压反应釜中反应,反应温度25℃,反应时间为1.5h,氢气压力为5.0MPa,搅拌速率为500rpm。测得环戊酮加氢的转化率为62.8%,环戊醇的选择性达100%。
实施例4
该实施例凸显氨水处理条件的变化对催化活性的影响,即改变实施例1中所用活性炭的氨水处理条件,采用100mL 10%的氨水溶液与1g活性炭混合,80℃加热下持续搅拌3h。降至室温后过滤洗涤至中性,80℃真空干燥12h。将干燥后的活性炭在氩气气氛下300℃焙烧3h,氩气流量为20mL/min,升温速率为5℃/min,其余同实施例1,制得所述氨水预处理活性炭负载三元金属催化剂。
采用本实施例中所制得的催化剂用于环戊酮加氢反应:催化剂投料量/底物为0.0lg/mL,在间歇式高压反应釜中反应,反应温度25℃,反应时间为1.5h,氢气压力为5.0MPa,搅拌速率为500rpm。测得环戊酮加氢的转化率为88.1%,环戊醇的选择性达100%。
实施例5
采用100mL 5%的氨水溶液与1g活性炭混合,60℃加热下持续搅拌3h。降至室温后过滤洗涤至中性,80℃真空干燥12h。将干燥后的活性炭在氩气气氛下300℃焙烧3h,氩气流量为20mL/min,升温速率为5℃/min。
称取0.018g的硝酸锶,0.035g的水合草酸铌和0.8g PVP,放入50mL去离子水中,搅拌30min后用氢氧化钠调节pH=10,加入0.6g的上述经氨水预处理的活性炭与6mL水合肼,水合肼的滴加速度为10滴/min,持续搅拌3h后过滤洗涤至中性,接着经80℃真空干燥12h后,在氢气中以5℃/min升温至500℃,氢气流量为80mL/min,恒温3h后降至室温,制得Nb-Sr/C。
称取0.015g的水合偏钨酸铵放入50mL去离子水中,搅拌30min。将上述Nb-Sr/C放入上述溶液中,持续搅拌2h后用氨水调节pH=10,在冰水浴的条件下滴加3mL水合肼,水合肼的滴加速度为10滴/min,持续搅拌2h后过滤洗涤至中性,在80℃真空干燥12h。将干燥后的催化剂在氢气气氛下以5℃/min升至500℃,恒温3h后降至室温,氢气流量为50mL/min,制得所述氨水预处理活性炭负载三元金属催化剂。
采用本实施例中所制得的催化剂用于环戊酮加氢反应:催化剂投料量/底物为0.01g/mL,在间歇式高压反应釜中反应,反应温度40℃,反应时间为2h,氢气压力为5.0MPa,搅拌速率为500rpm。测得环戊酮加氢的转化率为30.9%,环戊醇的选择性达99.4%。
实施例6
采用100mL 5%的氨水溶液与1g活性炭混合,60℃加热下持续搅拌3h。降至室温后过滤洗涤至中性,80℃真空干燥12h。将干燥后的活性炭在氩气气氛下300℃焙烧3h,氩气流量为20mL/min,升温速率为5℃/min。
称取0.025g的醋酸钙,0.015g醋酸铟和0.3g CTAB,放入50mL去离子水中,搅拌30min后用氢氧化钠调节pH=10,加入0.6g的上述经氨水预处理的活性炭与6mL水合肼,水合肼的滴加速度为10滴/min,持续搅拌3h后过滤洗涤至中性,接着经80℃真空干燥12h后,在氢气中以2℃/min升温至200℃,氢气流量为40mL/min,恒温3h后降至室温,制得In-Ca/C。
称取0.02g的水合三氯化钌放入50mL去离子水中,搅拌30min。将上述In-Ca/C放入上述溶液中,持续搅拌2h后用逐滴加入氨水至pH=10,加入10mL 8mol/L的抗坏血乙酸水溶液,持续搅拌2h后过滤洗涤至中性,在80℃真空干燥12h。将干燥后的催化剂在氢气气氛下以2℃/min升至300℃,恒温2h后降至室温,氢气流量为80mL/min,制得所述氨水预处理活性炭负载三元金属催化剂。
采用本实施例中所制得的催化剂用于环戊酮加氢反应:催化剂投料量/底物为0.01g/mL,在间歇式高压反应釜中反应,反应温度25℃,反应时间为2h,氢气压力为5.0MPa,搅拌速率为500rpm。测得环戊酮加氢的转化率为77.4%,环戊醇的选择性达100%。
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (10)
1.一种氨水预处理活性炭负载三元金属催化剂,其特征在于:以经氨水预处理的活性炭为载体,其上负载有贵金属元素、过渡金属元素和助剂碱土金属元素,其中,贵金属元素选自W、Re和Ru,过渡金属元素选自Nb、In和Pb,助剂碱土金属元素选自Ba、Ca和Sr;
上述氨水预处理包括:使用氨水溶液与活性炭进行混合搅拌并加热,氨水溶液浓度为5%-15%,处理温度为50-100℃,处理时间为1-6h,降至室温后用去离子水过滤并洗涤至中性,80℃真空干燥12h后在氩气气氛下200-400℃焙烧1-3h。
2.如权利要求1所述的一种氨水预处理活性炭负载三元金属催化剂,其特征在于:所述氩气气氛中的氩气的流量为20-50mL/min。
3.如权利要求2所述的一种氨水预处理活性炭负载三元金属催化剂,其特征在于:所述焙烧的升温速率为2-10℃/min。
4.如权利要求1至3中任一权利要求所述的一种氨水预处理活性炭负载三元金属催化剂,其特征在于:所述贵金属元素的负载量为0.1-1.5wt.%,所述过渡金属元素的负载量为0.5-2.5wt.%,所述助剂碱土金属元素的负载量为0.2-1.5wt.%。
5.权利要求1至4中任一权利要求所述的氨水预处理活性炭负载三元金属催化剂在环戊酮加氢制环戊醇中的应用。
6.如权利要求5所述的应用,其特征在于:采用间歇式高压釜液相加氢过程,不使用溶剂。
7.如权利要求6所述的应用,其特征在于:所述间歇式高压釜液相加氢过程中,氢气压力为0.5-5.5MPa,反应操作温度为室温20-40℃,催化剂投料量/底物为0.001-0.01g/mL,反应时间为0.5-2h。
8.一种环戊酮加氢制环戊醇的方法,其特征在于:采用权利要求1至3中任一权利要求所述的氨水预处理活性炭负载三元金属催化剂。
9.如权利要求8所述的方法,其特征在于:采用间歇式高压釜液相加氢过程,不使用溶剂。
10.如权利要求9所述的方法,其特征在于:所述间歇式高压釜液相加氢过程中,氢气压力为0.5-5.5MPa,反应操作温度为室温20-40℃,催化剂投料量/底物为0.001-0.01g/mL,反应时间为0.5-2h。
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