CN114853567B - 一种二氧化碳转化制备低碳醇催化剂及其制备方法和应用 - Google Patents
一种二氧化碳转化制备低碳醇催化剂及其制备方法和应用 Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 49
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 239000010941 cobalt Substances 0.000 abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001869 cobalt compounds Chemical class 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 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 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- -1 carbon alcohols Chemical class 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000000366 colloid method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 239000003921 oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- 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
- B01J23/8892—Manganese
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/83—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 rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- 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
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
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Abstract
本发明公开了一种二氧化碳转化制备低碳醇催化剂及其制备方法和应用,属于二氧化碳资源化利用技术领域。所述制备方法为:将混合均匀的钴单质、钴化合物和/或催化剂载体经机械球磨后进行热处理,热处理完成后即得催化剂产品。本发明提供的一种二氧化碳转化制备低碳醇催化剂的制备方法,以钴单质和钴的氧化物或氢氧化物为原料,在机械球磨的作用下将强化单质钴和钴化合物的相互作用,创造Co0‑Cox+双位点,这些双位点可催化醇的生成和碳链的生长,极大地促进了低碳醇的选择性,低碳醇选择性高于90%;所述制备方法具有废液少、成本低廉和过程简单等特点,具有良好应用前景。
Description
技术领域
本发明属于二氧化碳资源化利用技术领域,具体涉及一种二氧化碳转化制备低碳醇的催化剂及其制备方法和应用。
背景技术
近年来,二氧化碳的大量排放造成了全球暖化,并威胁了人类发展的可持续性。因此,减少二氧化碳的排放和降低大气中二氧化碳浓度以减缓全球变暖对人类的可持续发展有着极其重要的意义。捕集二氧化碳并将其转化成具有高附加值的燃料和化学品是减少二氧化碳排放和降低大气中二氧化碳浓度的关键手段。其中,低碳醇,如乙醇、丙醇和丁醇等被广泛用作替代燃料以及化工过程的溶剂和原料,具有很大的市场需求。因此将捕获的二氧化碳转化为低碳醇不仅有利于减缓全球暖化,而且有望创造巨大的荆棘效益。
然而,目前二氧化碳加氢制备低碳醇的过程中低碳醇的选择性较低,阻碍了其进一步工业应用。解决该问题的关键是通过优化催化剂的组分基制备方法开发具有高选择性的催化剂。
CN113751062A开了一种用于二氧化碳加氢制乙醇的多孔铜基催化剂及其制备方法,包括以下步骤:将模板剂、铜的可溶性盐溶于溶剂中,通过等体积浸渍法沉积在分子筛上,干燥、焙烧得负载分子筛;将负载分子筛和强碱溶液反应,反应后脱除模板剂,干燥,得样品;将铝源、硅源、强碱、模板剂、样品混合,得凝胶包埋体,然后陈化、干燥得干凝胶;将干凝胶晶化,然后洗涤、干燥、焙烧得铜基催化剂。该催化剂应用于二氧化碳加氢制乙醇,乙醇的选择性低于80%。
CN111434382A公开一种载体负载型氧化钒促进的Rh基催化剂及其制备方法和应用,以分子筛为载体,负载活性组分Rh,V为助剂。该催化剂制备时,采用共浸渍法,将载体浸置于氯化铑,偏钒酸铵的草酸水溶液中,干燥焙烧,得到催化剂。该催化剂适用于二氧化碳及一氧化碳加氢制乙醇反应,但乙醇的选择性低于30%。此外,Rh基催化剂具有价格昂贵,且该制备过程复杂繁琐。
CN111185160A公开了一种负载型催化剂及其制备方法,该催化剂以贵金属Au为活性组分,通过胶体法固载于氧化物载体上,因此该催化剂能够可以提高贵金属的分散,提高了载体之间的相互作用,减少了金属团聚。通过该方法制备的催化剂在二氧化碳加氢反应,乙醇选择性达到94%,但是采用金基催化剂具有价格昂贵等缺点。
综上,目前二氧化碳加氢制备乙醇的催化剂存在乙醇选择性较低、成本高以及制备过程复杂等缺点。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种二氧化碳转化制备低碳醇的催化剂及其制备方法和应用,所述制备方法简单、成本低,所述催化剂在二氧化碳加氢催化制备低碳醇反应中对于低碳醇的选择性高。
为了实现上述目的,本发明采用如下技术方案:
一种二氧化碳转化制备低碳醇催化剂的制备方法,包括如下步骤:将混合均匀的钴单质、钴化合物和/或催化剂载体经机械球磨后进行热处理,热处理完成后即得催化剂产品。
作为本发明技术方案的进一步优选,钴化合物选自钴的氧化物或氢氧化钴中的一种或多种。
作为本发明技术方案的进一步优选,钴的氧化物选自一氧化钴、三氧化二钴、四氧化三钴中的一种或多种。
作为本发明技术方案的进一步优选,所述催化剂载体选自铁、锆、铝、铈、锌、锰、钛、铜、镁、硅、镍、钼、钨、钒、镧的氧化物或碳材料中的一种或几种的混合物。
作为本发明技术方案的进一步优选,钴单质、钴化合物及催化剂载体的质量用量比为0.5~95:0.5~95:0.5~95。
作为本发明技术方案的进一步优选,机械球磨使用球磨机进行处理,所述球磨机选自行星式球磨机、罐装式球磨机、振动式磨矿机、搅拌式球磨机、针磨机、滚轧机或砂磨机中的一种或多种。
作为本发明技术方案的进一步优选,机械球磨中球磨罐选自不锈钢球磨罐、聚四氟乙烯球磨罐、玛瑙球磨罐、尼龙球磨罐、刚玉球磨罐、二氧化锆球磨罐中的一种或多种。
作为本发明技术方案的进一步优选,机械球磨中使用的研磨球选自不锈钢研磨球、氧化铝研磨球、玛瑙研磨球或氧化锆研磨球中的一种或几种。
作为本发明技术方案的进一步优选,机械球磨转速为10~1500r/min,机械球磨时间为0.5~72h。
作为本发明技术方案的进一步优选,热处理温度为20~800℃,热处理时间为0.5~48h。
同时,本发明还请求保护上述方法制备得到的催化剂。
同时,本发明还请求保护上述催化剂在二氧化碳加氢催化制备低碳醇中的应用。
与现有技术相比,本发明具有如下有益效果:
(1)本发明提供的一种二氧化碳转化制备低碳醇催化剂的制备方法,以钴单质和钴的氧化物或氢氧化物为原料,在机械球磨的作用下将强化单质钴和钴化合物的相互作用,创造Co0-Cox+双位点,这些双位点可催化醇的生成和碳链的生长,极大地促进了低碳醇的选择性,低碳醇选择性高于90%。
(2)本发明提供的一种二氧化碳转化制备低碳醇催化剂的制备方法,创造性地采用了机械球磨处理催化剂原料,使得颗粒尺寸下降,表面形成大量缺陷,为二氧化碳吸附提供了大量的位点,因此极大地促进了二氧化碳的转化率,其转化率高于20%。
(3)本发明提供的一种二氧化碳转化制备低碳醇催化剂的制备方法,以机械球磨和热处理为主,热处理可进一步强化单质钴和钴化合物的相互作用,调控钴单质和化合物的含量,该工艺简单,在制备过程中无需溶剂,不产生废液,实现零排放,避免了因为废液处理所产生的成本,成本相对较低。
具体实施方式
下面将结合本发明实施方式,对本发明实施方式中的技术方案进行清楚、完整地描述,显然,所描述的实施方式仅仅是本发明一部分实施方式,而不是全部的实施方式。基于本发明中的实施方式,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式,都属于本发明保护的范围。
如无特殊说明外,本发明中所有商品或试剂均通过市场渠道购买。
实施例1
一种二氧化碳转化制备低碳醇催化剂的制备方法,步骤如下:
(1)将0.5g Co、0.5g Co3O4和9g Al2O3混合,得混合物;
(2)将步骤(1)中所得混合物和250g刚玉研磨球置于500mL的刚玉研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速100r/min,球磨70h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于500℃的氮气中热处理5h;待热处理结束,即得催化剂产品。
在浆态床反应器中进行催化剂性能测试。
实施例2
一种二氧化碳转化制备低碳醇催化剂的制备方法,步骤如下:
(1)将2g Co、1g Co(OH)2和7g MoO3混合,得混合物;
(2)将步骤(1)中所得混合物和250g ZrO2研磨球置于500mL的二氧化锆研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速800r/min,球磨24h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于800℃的氩气中热处理1h;待热处理结束,即得催化剂产品。
在固定床反应器中进行催化剂性能测试。
实施例3
一种二氧化碳转化制备低碳醇催化剂的制备方法,步骤如下:
(1)将4g Co、4g CoO和2g MnO混合,得混合物;
(2)将步骤(1)中所得混合物和250g刚玉研磨球置于500mL的尼龙研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入滚筒式球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速200r/min,球磨50h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于500℃的一氧化碳中热处理3h;待热处理结束,即得催化剂产品。
在浆态床反应器中进行催化剂性能测试。
实施例4
一种二氧化碳转化制备低碳醇催化剂的制备方法,步骤如下:
(1)将2g Co、6g CoO和2g SiO2混合,得混合物;
(2)将步骤(1)中所得混合物和250g不锈钢研磨球置于500mL的不锈钢研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速800r/min,球磨0.5h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于50℃的空气中热处理48h;待热处理结束,即得催化剂产品。
在固定床反应器中进行催化剂性能测试。
实施例5
一种二氧化碳转化制备低碳醇催化剂的制备方法,步骤如下:
(1)将4g Co、4g Co3O4和4g La2O3混合,得混合物;
(2)将步骤(1)中所得混合物和250g ZrO2研磨球置于500mL的二氧化锆研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星式球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速400r/min,球磨20h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于250℃的氢气中热处理3h;待热处理结束,即得催化剂产品。
在浆态床反应器中进行催化剂性能测试。
实施例6
一种二氧化碳转化制备低碳醇催化剂的制备方法,步骤如下:
(1)将5g Co、3g Co3O4和4g活性炭混合,得混合物;
(2)将步骤(1)中所得混合物和250g ZrO2研磨球置于500mL的二氧化锆研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星式球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速300r/min,球磨60h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于700℃的氮气中热处理3h;待热处理结束,即得催化剂产品。
在浆态床反应器中进行催化剂性能测试。
实施例7
一种二氧化碳转化制备低碳醇催化剂的制备方法,步骤如下:
(1)将3g Co、5g Co(OH)2和4g ZrO2混合,得混合物;
(2)将步骤(1)中所得混合物和250g ZrO2研磨球置于500mL的二氧化锆研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星式球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速400r/min,球磨30h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于500℃的一氧化碳中热处理3h;待热处理结束,即得催化剂产品。
在固定床反应器中进行催化剂性能测试。
对比例1
一种二氧化碳转化制备低碳醇催化剂的制备方法,步骤如下:
(1)将0.5g Co、9.5g CoO混合,得混合物;
(2)将步骤(1)中所得混合物和250g不锈钢研磨球研磨球置于500mL的聚四氟乙烯研磨罐,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速400r/min,球磨5h;球磨结束后取出混合物,即得催化剂产品。
在固定床反应器中进行催化剂性能测试。
测试例
固定床反应器:将0.3g制备得到的催化剂与2g SiC混合后置于反应器中,原料气(20v%二氧化碳、70v%氢气、10v%氮气混合物)以一定流量流过催化剂床层,采用的空速为2升/克催化剂/小时,将反应压力逐步升高至5MPa,将反应温度逐步升高至250℃开始反应,进行为期100h的性能测试,反应器出口产物保温在150℃,通入色谱进行在线分析。
浆态床反应器:将3克制备得到的催化剂与100mL高沸点蜡油在室温下混合,随后将该混合物转移至1L的连续搅拌反应器中。原料气(20v%二氧化碳、70v%氢气、10v%氮气混合物)以一定流量通入反应器,采用的空速为2升/克催化剂/小时,将反应压力逐步升高至5.0MPa,将反应温度逐步升高至230℃开始反应,反应器出口产物保温在150℃,通入色谱进行在线分析。
按照以下公式计算二氧化碳转化率和产物选择性:
二氧化碳转化率=(进口二氧化碳摩尔数-出口二氧化碳摩尔数)/进口二氧化碳摩尔数*100%;
产物选择性=出口产物摩尔数*产物中碳原子数/(进口二氧化碳摩尔数-出口二氧化碳摩尔数)*100%。
测试结果见表1所示。
表1催化剂催化性能测试结果
从表1中可以看到,本发明制备得到的催化剂能够较好地实现二氧化碳加氢制备低碳醇的技术效果,以实施例6为例,二氧化碳的转化率为22%,总醇选择性高达93%;其中乙醇的选择性高达88%,甲醇和乙醇的选择性之和高达90%。
本发明通过上述实施例来说明本发明的技术构思,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品个别原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (3)
1.一种二氧化碳转化制备低碳醇催化剂的制备方法,其特征在于,步骤为:
(1)将5g Co、3g Co3O4和4g活性炭混合,得混合物;
(2)将步骤(1)中所得混合物和250g ZrO2研磨球置于500mL的二氧化锆研磨罐中,并在研磨罐中通入氮气将空气置换;将研磨罐放入行星式球磨机中进行研磨;设置球磨的条件为:每隔1h顺时针和逆时针方向交替旋转,转速300r/min,球磨60h;球磨结束后取出混合物;
(3)将步骤(2)中球磨完后的混合物置于700℃的氮气中热处理3h;待热处理结束,即得催化剂产品。
2.权利要求1所述方法制备得到的催化剂。
3.权利要求2所述催化剂在二氧化碳加氢催化制备低碳醇中的应用。
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