CN116899559A - 一种双金属炭黑负载型催化剂及其应用 - Google Patents
一种双金属炭黑负载型催化剂及其应用 Download PDFInfo
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- CN116899559A CN116899559A CN202310928517.6A CN202310928517A CN116899559A CN 116899559 A CN116899559 A CN 116899559A CN 202310928517 A CN202310928517 A CN 202310928517A CN 116899559 A CN116899559 A CN 116899559A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000006229 carbon black Substances 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 claims abstract description 22
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 14
- 239000007791 liquid phase Substances 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 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
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
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- 239000008367 deionised water Substances 0.000 description 12
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- 239000005457 ice water Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 6
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- -1 Cycloheptyl alcohol Chemical compound 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 235000019441 ethanol Nutrition 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
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000007799 cork Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 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
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- XBMSSMOTGOJLBZ-UHFFFAOYSA-N zirconium(4+) tetranitrate hydrate Chemical compound O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XBMSSMOTGOJLBZ-UHFFFAOYSA-N 0.000 description 1
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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Abstract
本发明公开了一种双金属炭黑负载型催化剂及其应用，其以经过预氧化处理的炭黑为载体，其上负载有第一金属元素和第二金属元素，其中，第一金属元素选自Rh、Re和Ag，第二金属元素选自V、Zn和Zr。本发明应用于环庚酮催化加氢制环庚醇，在环庚酮的催化转化达100％的同时，产物环庚醇的选择性可达100％，看极大减轻产物的分离提纯负担，降低生产成本；催化反应过程不使用溶剂，操作温度低，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，具体涉及一种双金属炭黑负载型催化剂及其应用。
背景技术
环庚醇，又名软木醇，是一种重要的化工原料，可用于精细有机合成的上游原料，属于一种重要的医药及材料中间体。环庚醇可以由环庚酮加氢制得，目前还未见有环庚酮加氢制环庚醇的相关专利。曾有专利文献公开酮类化合物加氢制醇类化合物的催化剂及工艺。
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。
综上所述，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，提供一种双金属炭黑负载型催化剂。
本发明的另一目的在于提供上述双金属炭黑负载型催化剂的应用。
本发明的技术方案如下：
一种双金属炭黑负载型催化剂，其特征在于：以炭黑为载体，其上负载有第一金属元素和第二金属元素，其中，第一金属元素选自Rh、Re和Ag，第二金属元素选自V、Zn和Zr；
上述双金属炭黑负载型催化剂的制备过程包括：先将第二金属元素负载于炭黑上，再将第一金属元素负载于活性炭上。具体的负载方法为：采用金属前驱体的盐溶液与炭黑混合浸泡搅拌，加入表面活性剂并调节金属前驱体的盐溶液pH值至0.5-5.5或8-13，并加入化学还原剂进行还原，过滤洗涤至中性后在75-85℃真空干燥10-12h；在分步负载第二金属元素和第一金属元素后均要在氢气气氛中进行焙烧退火处理。
在本发明的一个优选实施方案中，所述金属前驱体的盐选自硝酸盐，乙酰丙酮盐和氯化物。
在本发明的一个优选实施方案中，所述表面活性剂选自聚乙烯吡咯烷酮和聚乙烯吡咯烷醇，所述化学还原剂选自水合肼、甲醛溶液和抗坏血乙酸。
在本发明的一个优选实施方案中，所述第一金属元素的负载量为0.1-1.5wt.％，所述第二金属元素的负载量为0.3-2.0wt.％。
上述双金属炭黑负载型催化剂在环庚酮加氢制环庚醇中的应用。
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1-4.5MPa，反应温度为20-80℃，催化剂投料量/底物为0.001-0.01g/mL，反应时间为0.5-2h。
一种环庚酮加氢制环庚醇的方法，采用上述双金属炭黑负载型催化剂。
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1-4.5MPa，反应温度为20-80℃，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、本发明的双金属炭黑负载型催化剂应用于环庚酮液相加氢过程的操作温度较低，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、本发明在环庚酮的催化转化达100％的同时，产物环庚醇的选择性可达100％，可极大减轻产物的分离提纯负担，降低生产成本。
4、本发明的双金属炭黑负载型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
称取0.02g的水合硝酸锆，放入50mL去离子水中，加入0.6g的炭黑，搅拌3h后用氨水调节pH＝10，加入5mL无水乙醇和0.3g聚乙烯吡咯烷醇，持续搅拌1h后在冰水浴的条件下滴加5mL的水合肼，水合肼的滴加速度为10滴/min。滴加完毕后持续搅拌2h，过滤洗涤至中性，80℃真空干燥12h。最后在氢气气氛中以5℃/min升温至400℃，气体流量为80mL/min，恒温3h降至室温，制得Zr/C。
称取0.012g的硝酸银放入50mL去离子水中，搅拌30min。将上述Zr/C放入上述溶液中，用氢氧化钠调节pH＝10，持续搅拌1h后在冰水浴的条件下滴加3mL水合肼,滴加速度为10滴/min，搅拌2h后过滤洗涤至中性，80℃真空干燥12h。最后在氢气气氛中以2℃/min升温至300℃，气体流量为50mL/min，恒温3h后降至室温，制得双金属炭黑负载型催化剂。
将本实施例中所制得的双金属炭黑负载型催化剂用于环庚酮加氢制环庚醇：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80℃，反应时间为2h，氢气压力为4.5MPa，搅拌速率为500rpm。测得环庚酮加氢的转化率为32.9％，环庚醇的选择性达100％。
实施例2
称取0.015g的偏钒酸铵，放入50mL去离子水中，加入0.6g的炭黑，搅拌3h后用氢氧化钠调节pH＝9，加入5mL无水乙醇和0.3g聚乙烯吡咯烷酮，持续搅拌1h后在室温条件下滴加10mL的35％甲醛水溶液，滴加速度为10滴/min，持续搅拌3h后过滤洗涤至中性，80℃真空干燥12h。最后在氢气气氛中以5℃/min升温至500℃，气体流量为80mL/min，恒温3h降至室温，制得V/C。
称取0.012g的硝酸银放入50mL去离子水中，搅拌30min。将上述V/C放入上述溶液中，用氢氧化钠调节pH＝10，持续搅拌1h后在冰水浴条件下滴加3mL水合肼,滴加速度为10滴/min，搅拌2h后过滤洗涤至中性，80℃真空干燥12h。最后在氢气气氛中以2℃/min升温至200℃，气体流量为50mL/min，恒温3h后降至室温，制得所述双金属炭黑负载型催化剂。
将本实施例中所制得的双金属炭黑负载型催化剂用于环庚酮加氢制环庚醇：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80℃，反应时间为2h，氢气压力为4.5MPa，搅拌速率为500rpm。测得环庚酮加氢的转化率为45.4％，环庚醇的选择性达98.9％。
实施例3
称取0.03g的六水合硝酸锌，放入50mL去离子水中，加入0.6g的炭黑，搅拌3h后用氢氧化钠调节pH＝10，加入5mL无水乙醇和0.3g聚乙烯吡咯烷醇，持续搅拌1h后在冰水浴的条件下滴加5mL的水合肼，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，80℃真空干燥12h。最后在氢气气氛中以5℃/min升温至400℃，气体流量为80mL/min，恒温3h降至室温，制得Zn/C。
称取0.015g的水合氯化铑，溶于50mL去离子水中。将上述Zn/C放入上述溶液中，用氢氧化钠调节pH＝10，加入10mL 5mol/L的抗坏血乙酸水溶液，持续搅拌3h后利用红外灯快速干燥，接着进行80℃真空干燥12h。最后在氢气气氛中以2℃/min升温至200℃，气体流量为50mL/min，恒温3h后降至室温，制得所述双金属炭黑负载型催化剂。
将本实施例中所制得的双金属炭黑负载型催化剂用于环庚酮加氢制环庚醇：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1.5h，氢气压力为4.5MPa，搅拌速率为500rpm。测得环庚酮加氢的转化率为79.6％，环庚醇的选择性达100％。
实施例4
称取0.015g的偏钒酸铵，放入50mL去离子水中，加入0.6g的炭黑，搅拌3h后用氢氧化钠调节pH＝8，加入5mL无水乙醇和0.3g聚乙烯吡咯烷酮，持续搅拌1h后在室温条件下滴加10mL的35％的甲醛水溶液，滴加速度为10滴/min，持续搅拌3h后过滤洗涤至中性，80℃真空干燥12h。最后在氢气气氛中以5℃/min升温至500℃，气体流量为80mL/min，恒温3h降至室温，制得V/C。
称取0.012g的高铼酸铵放入50mL去离子水中，搅拌30min。将上述V/C放入上述溶液中，用氢氧化钠调节pH＝10，持续搅拌1h后在冰水浴条件下滴加3mL水合肼，滴加速度为10滴/min，持续搅拌2h后过滤洗涤至中性，80℃真空干燥12h。最后在氢气气氛中以2℃/min升温至300℃，气体流量为50mL/min，恒温3h后降至室温，制得所述双金属炭黑负载型催化剂。
将本实施例中所制得的双金属炭黑负载型催化剂用于环庚酮加氢制环庚醇：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1.5h，氢气压力为4.5MPa，搅拌速率为500rpm。测得环庚酮加氢的转化率为100％，环庚醇的选择性达99.2％。
实施例5
称取0.025g的六水合硝酸锌，放入50mL去离子水中，加入0.6g的炭黑，搅拌3h后用氢氧化钠调节pH＝10，加入5mL无水乙醇和0.3g聚乙烯吡咯烷醇，持续搅拌1h后在冰水浴的条件下滴加5mL水合肼，滴加速度为10滴/min。持续搅拌3h后过滤洗涤至中性，80℃真空干燥12h。最后在氢气气氛中以5℃/min升温至500℃，气体流量为80mL/min，恒温3h降至室温，制得Zn/C。
称取0.012g的高铼酸铵放入50mL去离子水中，搅拌30min。将上述Zn/C放入上述溶液中，用氢氧化钠调节pH＝10，持续搅拌1h后在冰水浴的条件下滴加3mL水合肼，滴加速度为10滴/min。持续搅拌3h后过滤洗涤至中性，80℃真空干燥12h。最后在氢气气氛中以2℃/min升温至300℃，气体流量为50mL/min，恒温3h后降至室温，制得所述双金属炭黑负载型催化剂。
将本实施例中所制得的双金属炭黑负载型催化剂用于环庚酮加氢制环庚醇：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1.5h，氢气压力为4.5MPa，搅拌速率为500rpm。测得环庚酮加氢的转化率为100％，环庚醇的选择性达100％。
实施例6
称取0.015g的偏钒酸铵，放入50mL去离子水中，加入0.6g的炭黑，搅拌3h后用氢氧化钠调节pH＝10，加入5mL无水乙醇和0.1g聚乙烯吡咯烷醇，持续搅拌1h后在室温条件下滴加10mL的35％甲醛水溶液，滴加速度为10滴/min。持续搅拌3h后过滤洗涤至中性，80℃真空干燥12h。最后在氢气气氛中以5℃/min升温至500℃，气体流量为80mL/min，恒温3h降至室温，制得V/C。
称取0.015g的水合氯化铑，溶于50mL去离子水中。将上述V/C放入上述溶液中，用氢氧化钠调节pH＝10，加入10mL 5mol/L抗坏血乙酸水溶液，室温搅拌12h后利用红外灯快速干燥，并进行80℃真空干燥12h。最后在氢气气氛中以2℃/min升温至400℃，气体流量为50mL/min，恒温3h后降至室温，制得所述双金属炭黑负载型催化剂。
将本实施例中所制得的双金属炭黑负载型催化剂用于环庚酮加氢制环庚醇：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4.5MPa，搅拌速率为500rpm。测得环庚酮加氢的转化率为90.6％，环庚醇的选择性达99.5％。
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)
1.一种双金属炭黑负载型催化剂，其特征在于：以炭黑为载体，其上负载有第一金属元素和第二金属元素，其中，第一金属元素选自Rh、Re和Ag，第二金属元素选自V、Zn和Zr；
上述双金属炭黑负载型催化剂的制备包括：先将第二金属元素负载于炭黑上，再将第一金属元素负载于活性炭上，具体的负载方法为：采用金属前驱体的盐溶液与炭黑混合浸泡搅拌，加入表面活性剂并调节金属前驱体的盐溶液的pH值至0.5-5.5或8-13，加入化学还原剂进行还原，过滤洗涤至中性后在75-85℃真空干燥10-12h；在分步负载第二金属元素和第一金属元素后均要进行氢气气氛下的焙烧退火处理。
2.如权利要求1所述的一种双金属炭黑负载型催化剂，其特征在于：所述金属前驱体的盐选自硝酸盐，乙酰丙酮盐和氯化物。
3.如权利要求1所述的一种双金属炭黑负载型催化剂，其特征在于：所述表面活性剂选自聚乙烯吡咯烷酮和聚乙烯吡咯烷醇，所述化学还原剂选自水合肼、甲醛溶液和抗坏血乙酸。
4.如权利要求1至3中任一权利要求所述的一种双金属炭黑负载型催化剂，其特征在于：所述第一金属元素的负载量为0.1-1.5wt.％，所述第二金属元素的负载量为0.3-2.0wt.％。
5.权利要求1至4中任一权利要求所述的双金属炭黑负载型催化剂在环庚酮加氢制环庚醇中的应用。
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1-4.5MPa，反应温度为20-80℃，催化剂投料量/底物为0.001-0.01g/mL，反应时间为0.5-2h。
8.一种环庚酮加氢制环庚醇的方法，其特征在于：采用权利要求1至4中任一权利要求所述的双金属炭黑负载型催化剂。
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1-4.5MPa，反应温度为20-80℃，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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