CN112169805A - Cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas - Google Patents
Cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas Download PDFInfo
- Publication number
- CN112169805A CN112169805A CN202011113776.6A CN202011113776A CN112169805A CN 112169805 A CN112169805 A CN 112169805A CN 202011113776 A CN202011113776 A CN 202011113776A CN 112169805 A CN112169805 A CN 112169805A
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- Prior art keywords
- catalyst
- cobalt
- gallium
- corrosion
- synthesis gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- QWYVKZJDGBMHFE-UHFFFAOYSA-N cobalt gallium Chemical compound [Co].[Ga] QWYVKZJDGBMHFE-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 93
- 230000007797 corrosion Effects 0.000 claims description 82
- 238000005260 corrosion Methods 0.000 claims description 82
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- 229910052759 nickel Inorganic materials 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000006056 electrooxidation reaction Methods 0.000 claims description 13
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 229940044658 gallium nitrate Drugs 0.000 claims description 8
- 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 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000002045 lasting effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-OUBTZVSYSA-N nickel-60 atom Chemical compound [60Ni] PXHVJJICTQNCMI-OUBTZVSYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003513 alkali Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- -1 carbon alcohols Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/83—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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/613—
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- B01J35/657—
-
- 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
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/114—Making porous workpieces or articles the porous products being formed by impregnation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—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 oxides of carbon exclusively
- C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention provides a cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas, which is an integral three-dimensional porous catalyst, and has the characteristics of excellent mechanical strength, high heat transfer performance, low local hot spot and effective improvement of a solid-phase mass transfer process compared with a powder catalyst, wherein the specific surface area of the catalyst is 20-50m2The compressive strength of the catalyst is 2-4 MPa.
Description
Technical Field
The invention relates to a cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas, belongs to the field of electrochemical dealloying for preparing porous materials, and particularly relates to preparation of low-carbon mixed alcohol by perovskite catalytic hydrogenation.
Technical Field
First, low carbon alcohols, which refer to alcohols containing two or more carbon atoms, are receiving much attention because of their wide application in the chemical and polymer industries, such as raw materials and intermediates for synthesizing specific commercial products, and as an excellent gasoline additive, can increase the octane number of gasoline. Currently, they are obtained mainly by grain/sugar fermentation (e.g. ethanol and isobutanol) or by hydration of petroleum derived olefins (e.g. heavy alcohols). If the low-carbon alcohol can be directly prepared from the synthesis gas (CO + H2), the grain can be saved, and the abundant coal and natural gas resources in China can be fully utilized, so that the contradiction of industrial consumption of the grain in China and the shortage of petroleum resources is relieved. On the other hand, the global climate environment is deteriorated by the greenhouse effect, and the global climate environment is increasingly emphasized on the reduction of carbon dioxide gas and the comprehensive utilization thereof. In the research of comprehensive utilization and changing waste into valuable, the direct preparation of the low-carbon alcohol by carbon dioxide hydrogenation is considered to be one of economic and effective methods.
As is known, the industrial production of low carbon alcohol from synthesis gas has not been realized for decades, and the development of excellent catalysts with high activity and good stability has been the goal of the present researchers because the catalysts for the reaction of producing low carbon alcohol from synthesis gas cannot meet the industrial demand. The catalysts used in the reaction of preparing low-carbon alcohol from synthesis gas are mainly classified into four types, namely a catalyst represented by a precious metal Rh group, a catalyst including a Mo group, a modified methanol synthesis catalyst and a modified Fischer-Tropsch synthesis catalyst, wherein the modified F-T synthesis catalyst is prepared by adding another active component on the basis of the F-T synthesis catalyst to generate low-carbon alcohol, the active components of the F-T synthesis reaction mainly comprise three types, namely Fe, Co and Ni, and the modified Fischer-Tropsch catalyst most commonly comprises a Cu-Co group system and a Cu-Fe group system.
According to the structural characteristics of energy sources of rich coal, poor oil and less gas in China and the wide application of low carbon alcohol in the aspects of chemical industry, medicines and energy sources; the synthesis gas is prepared from coal, and the synthesis gas is used for preparing the low-carbon alcohol, so that the synthesis route has great significance and prospect. However, the route has not been industrialized after decades of research due to the fact that the catalyst cannot meet the industrial requirements. The preparation of low-carbon alcohol by using synthesis gas is a very complex reaction system, and has more side reactions and more miscellaneous products. Therefore, a good reaction catalyst for preparing low-carbon alcohol from synthesis gas needs to have good activity, high alcohol selectivity, excellent stability, good anti-carbon deposition and anti-sintering performance at the same time. In addition, the catalyst needs to have two active sites, one for dissociative adsorption of CO, i.e. hydrocarbon generation, and one for non-dissociative adsorption of CO, i.e. alcohol generation, which are cooperated to generate lower alcohol. Therefore, it is difficult to satisfy the above elements simultaneously. PTO is popular among researchers due to its characteristics of composition diversity, uniform mixing and the like. The catalyst can enable different ions to be uniformly mixed in the same compound molecule, and after the reduction, active species can migrate to the surface of the catalyst to be uniformly dispersed, thereby being beneficial to the improvement of activity. In addition, the PTO structure is beneficial to the synergistic effect among active species, can meet the requirement of the interaction among active components when applied to HAS reaction, and is greatly helpful for improving the selectivity of low-carbon alcohol. Therefore, we chose to use PTO as a precursor for the catalyst for the HAS reaction. However, pure PTO has a small surface area, which is not favorable for dispersion of active components, so how to increase the surface area of PTO is also one of the problems that we need to solve.
As for the patents: cobalt-gallium-based catalyst taking CN201710270774A perovskite type composite oxide as precursor, preparation and application thereof, wherein the catalyst is La1-ACo1-β-γGaβBγO3Wherein A is one or more of Y, Ce, K, Sr, Cs, Ca, Na or Ba; b is one or more of Rh, In, Mn, Cu, Ru, Ni or Fe; the value ranges of beta and gamma are respectively 0-0.3, 0.1-0.99 and 0-0.3, and gamma is not 0 at the same time. LaCo1-αGaαO3Or La1-ACo1-β-γGaβBγO3Loaded on a carrier and composed of LaCo1-αGaαO3Support or La1-ACo1-β-γGaβBγO3A support, wherein the support is SiO2、ZrO2、TiO2、CeO2、Al2O3、Y-ZrO2、CexTi1-xO2、CexZr1-xO2One or a combination of more of the above; LaCo1-αGaαO3Or La1-ACo1-β-γGaβBγO3The mass fraction value range in the catalyst is 5-40. As can be seen from the above, the carrier of the catalyst is SiO2、ZrO2、TiO2、CeO2、Al2O3、Y-ZrO2、CexTi1-xO2、CexZr1-xO2I.e. non-metallic inorganic materials, and as stated in the specification, the catalyst of this patent is in the powder state, which causes the catalyst to face the following technical problems: (1) troublesome in handling; (2) is not easy to form and the mechanical strength can not meet the requirement; (3) mass and heat transfer are greatly hindered, and the treatment efficiency is reduced; (4) the pressure drop difference between the front and the back of the catalyst bed is large, the energy consumption is increased, and the selection of the catalyst carrier needs to be improved urgently.
The porous metal is a porous material with a large number of directional or random holes dispersed therein, and the diameter of the holes is between about 2um and 25 mm. The porous metal material not only retains the conductivity, ductility, weldability and the like of the metal material, but also has the excellent characteristics of small specific gravity, large specific surface area, high specific strength, energy absorption, shock absorption, noise reduction, electromagnetic shielding, low heat conductivity and the like, and the conventional hierarchical porous material mainly comprises a micropore-mesopore material, a micropore-macropore material, a macropore-mesopore material, a micropore-mesopore-macropore material and a mesopore-mesopore material containing two or more different pore diameters. The main preparation methods comprise a template method, a hydrothermal method, a foaming method, a sol-gel method, a molten salt method and the like, and because the method usually relates to a chemical synthesis method in the synthesis process, the preparation steps are multiple, and the process is complex, the synthesis cost of the existing hierarchical pore material is high, the pore structure control difficulty is large, the process stability is poor, and the large-scale production is difficult. The dealloying method utilizes the potential difference of electrodes of different metal elements in the multi-element alloy to carry out free corrosion in electrolyte solutions such as acid and alkali or promote corrosion to remove relatively active components in the electrolyte solutions by applying voltage, and relatively inert components are reserved to form a bicontinuous open porous structure. The method is simple, convenient and feasible, is easy to repeat, is suitable for preparing the nano porous material on a large scale, and can realize the control of the pore diameter/pore wall size distribution of the porous material by controlling the processes of corrosion, subsequent heat treatment and the like.
Based on the above, there is a need to design a catalyst with very good activity, selectivity, stability, anti-carbon deposition and anti-sintering properties; meanwhile, the active sites of the catalyst can be catalyzed cooperatively, and the catalyst has the characteristics of good mechanical property, high heat conductivity and few hot spots.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a preparation method of a porous nickel-loaded perovskite catalyst for preparing low-carbon alcohol from synthesis gas, aiming at the defects of the traditional powder catalyst or porous block catalyst. The method has simple process and low cost, and the strength and catalytic activity of the obtained porous metal bulk catalyst are suitable for industrial popularization, and the specific contents are as follows:
a cobalt-gallium catalyst for preparing low-carbon alcohol from synthetic gas is LaCo1-αGaαO3Porous nickel, the alpha ranges from 0.3 to 0.45, the catalyst is a non-powder catalyst, wherein the pore size distribution of the porous nickel is between 5 and 30 mu m, and the specific surface area is between 30 and 60m2(ii)/g, porosity 50-70%, said LaCo1-αGaαO3The perovskite is uniformly loaded on the inner surfaces of the pore channels of the porous nickel, and the specific surface area of the catalyst is 20-50m2The compressive strength of the catalyst is 2-4 MPa.
The preparation steps of the catalyst are as follows:
the method comprises the following steps:
(1) preparing a Ni-Al alloy block:
(a) uniformly mixing 30-40wt.% of 1-5 μm nickel powder and 60-70wt.% of 5-10 μm aluminum powder;
(b)300-400 Mpa;
(c) sintering at high temperature in inert atmosphere or reducing atmosphere, wherein the sintering temperature is 1300-1400 DEG CoC, high temperature lasting for 1-3h, natural cooling,
the pressure maintaining time for press forming is 5-10 min; the inert atmosphere is N2The reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
This step should be noted:
the proportion and the size of the nickel and the aluminum powder directly influence the pore size distribution, the specific surface area and the porosity of porous nickel obtained subsequently, and the range of the invention is defined as follows: 30-40wt.%1-5 μm nickel powder, 60-70wt.%5-10 μm aluminum powder, preferably 33-38wt.% 2-3 μm nickel powder, 62-68wt.%,7-8 μm aluminum powder, most preferably 35wt.% 2-3 μm nickel powder, 65wt.%,7-8 μm aluminum powder.
The three-dimensional porous catalyst has certain compressibility and deformability, the volume and the size of the three-dimensional porous catalyst are larger than or equal to the size of the reactor, the exceeding range is not higher than 10 percent and cannot be lower than the size or the volume of the reactor, otherwise, the reactor has poor tightness, and reaction gas cannot effectively contact the catalyst.
Thirdly, the impurity degree and the stability of the alloy are determined by the sintering atmosphere, if oxygen is mixed, the Ni-Al alloy state is obviously influenced, and the influence of oxides on the alloy state is also obviously influenced.
And fourthly, the sintering temperature mainly influences the specific form of the alloy.
(2) Preliminary dealloying by chemical lye corrosion: the corrosive liquid used for preliminary dealloying by chemical alkaline corrosion is 1-2M NaOH aqueous solution, the corrosion time is 12-24h, and the temperature is 30-35oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
The primary de-alloying is mainly based on electroless corrosion, mainly based on the following considerations:
firstly, preliminary dealloying is electroless corrosion, namely, the electroless corrosion is completely eliminated, the electroless corrosion is mainly used for taking the electrified corrosion as an anode, and the Ni-Al alloy is used in the invention, wherein Al does not have corrosion reaction, but forms alumina due to anodic oxidation, or forms an oxide film on the Ni-Al alloy, thus not only a corrosion pore channel can not be formed, but also a protective film can be formed.
Secondly, the corrosive liquid of the electroless corrosion for preliminary alloy removal is sodium hydroxide, Al is known to be an amphoteric compound, both acid and alkali can carry out corrosion reaction, and the problem of selective corrosion is considered by only selecting the sodium hydroxide, so that only the Al in the sodium hydroxide is corroded without corroding Ni, and the corrosion is very important for the formation of the uniformity of the three-dimensional pore channel.
And thirdly, in the corrosion process, the reaction of aluminum and sodium hydroxide can generate hydrogen which can not be captured by naked eyes, and the ultrasonic wave of the hydrogen can obstruct the contact of the sodium hydroxide and the aluminum, so that the ultrasonic assistance must be added in the electroless corrosion process, and the diffusion and the separation of small bubbles are facilitated.
Fourthly, the concentration, the time and the temperature in the electroless corrosion process are obtained through orthogonal experiments, and the porous nickel aluminum material carrier is preliminarily obtained for optimizing the range.
(3) Deep dealloying by electrochemical acid corrosion: taking the nickel material obtained in the step (2) as an anode, taking a Pt sheet as a cathode, and taking 0.6-0.7M HNO3The corrosion voltage is 0.3-0.5V, the corrosion time is 2-3h, and the electrochemical corrosion temperature is normal temperature.
Attention is paid to:
the electrochemical corrosion is positioned after the electroless corrosion, and the steps can not be randomly reversed.
The electrochemical corrosion liquid is acid liquid, which can be sulfuric acid, nitric acid, phosphoric acid and oxalic acid, and the nitric acid is preferably selected in consideration of corrosion effect and corrosion rate, in addition, the acid liquid is adopted for corrosion in the electrochemical corrosion process, so that the preparation steps of the catalyst carrier can be reduced, namely, the preliminary corrosion and the deep corrosion directly do not need any cleaning and drying treatment, and certainly, if the preliminary corrosion nickel-aluminum material can be cleaned and air-dried by water and repeated for multiple times, the subsequent deep corrosion has the best porous structure, but for convenience of operation, the acid liquid can be selected to directly neutralize the alkali corrosion liquid to remove the adhesive film on the surface of the nickel-aluminum alloy.
And thirdly, the electrochemical corrosion is preferred because the aluminum can be removed by the electroless corrosion but can not be completely removed, at least within 12-24h of the invention, the aluminum can not be effectively removed by the electroless corrosion, and the existence of the aluminum can obviously reduce the porosity of a three-dimensional pore channel structure, so that the residual aluminum can be effectively removed by the subsequent electrochemical corrosion, and further, mesopores are effectively formed, the generation of the mesopores is favorable for improving the specific surface area of the porous nickel, and the pore size distribution of the obtained porous nickel is 5-30 μm, the specific surface area is 30-60m2/g, and the porosity is 50-70%.
The concentration and the voltage of the corrosive acid liquid are lower, the time is shorter, and the consideration of preventing the anodic oxidation of the aluminum is based on the premise of effective corrosion.
(4) Oxidation and activation: the oxidation activation is carried out for 5-10min under the condition of 40wt.% oxygen-air.
The porous material obtained at the moment is a porous nickel material and is used as a carrier of a subsequent catalyst, the carrier of the catalyst has certain binding force with an active component directly, and if the active component cannot be effectively loaded, the loss of catalytic activity can be caused.
(5) Preparing cobalt-gallium perovskite precursor solution: lanthanum nitrate, cobalt nitrate and gallium nitrate are sequentially mixed in a mixed solution of citric acid and ethylene glycol, wherein the molar ratio of La to Co to Ga to citric acid to ethylene glycol =1 (0.55-0.7) to (0.3-0.45) to 2.5 to 0.53, the step can select a proper perovskite bimetallic catalyst in the prior art, and LaCo is selected for the invention0.65Ga0.35O3Is an active component.
(6) Preparation of LaCo by dipping-high temperature roasting0.7Ga0.3O3Porous nickel catalyst: soaking the nickel material obtained in the step (4) in the cobalt-gallium perovskite precursor solution obtained in the step (5) for 12-24h at normal temperature, and then soaking at 80 deg.CoC, continuously stirring for 8 hours in a water bath kettle, and performing a high-temperature roasting processTemperature rising process is 3oC/min is increased to 120oC, preserving the heat for 12 hours, and then 2oC/min is increased to 650oC, preserving heat for 5-7h, naturally cooling along with a muffle furnace, and LaCo1-αGaαO3Porous nickel catalyst, said LaCo1-αGaαO3Porous nickel catalyst was passed through 3-5vol.% H before use2/N2Reducing for 3-5 h.
The scheme of the invention has the following beneficial effects:
(1) the three-dimensional porous nickel material is obtained through electroless preliminary dealloying and charged deep dealloying treatment, wherein macropores are favorable for gas mass transfer, mesopores are favorable for surface area improvement and active component loading, the pore diameter of porous nickel is distributed in a range of 5-30 mu m, and the specific surface area is 30-60m2G, porosity 50-70%.
(2) The catalyst carrier is metal, has high heat conductivity, and the metal characteristics determine that the catalyst carrier can effectively avoid the hot spot problem of a catalyst bed layer, avoid inactivation, is favorable for the stability of the catalyst, has high mechanical strength, and meets the basic requirements of a massive catalyst carrier.
(3) The shape and appearance of the catalyst carrier are obtained through alloying treatment, the shape and structure of the catalyst carrier are adjustable, the applicability is strong, the mechanical performance of the carrier is high, and the compressive strength of the catalyst is 2-4 Mpa.
(4) The activation treatment is favorable for improving the bonding strength of the active component of the catalyst and the carrier, the catalyst has excellent stability, the perovskite is uniformly loaded on the inner surface of the pore channel of the porous nickel, and the specific surface area of the catalyst is 20-50m2/g。
(5) Has higher selectivity and high activity and stability to low-carbon alcohol.
Detailed Description
Example 1
A Co-Ga catalyst for preparing low-carbon alcohol from synthetic gas is LaCo0.7Ga0.3O3A non-powder catalyst comprising the steps of:
(1) preparing a Ni-Al alloy block:
(a) uniformly mixing 30wt.% of 2-3 μm nickel powder and 70wt.% of 7-8 μm aluminum powder;
(b) pressing and molding under 300 Mpa;
(c) sintering at high temperature 1300 deg.C in inert atmosphereoC, high temperature lasting for 1h, natural cooling,
the pressure maintaining time of the compression molding is 5 min; the inert atmosphere is N2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
(2) Preliminary dealloying by chemical lye corrosion: the corrosive liquid used for preliminary dealloying by the corrosion of the chemical alkali liquor is 1M NaOH aqueous solution, the corrosion time is 12h, and the temperature is 30oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
(3) Deep dealloying by electrochemical acid corrosion: taking the nickel material obtained in the step (2) as an anode, taking a Pt sheet as a cathode and taking 0.6M HNO3The corrosion voltage is 0.3V, the corrosion time is 2h, and the electrochemical corrosion temperature is normal temperature.
(4) Oxidation and activation: the oxidation activation is oxidation under 40wt.% oxygen-air condition for 5 min.
(5) Preparing cobalt-gallium perovskite precursor solution: lanthanum nitrate, cobalt nitrate and gallium nitrate are sequentially mixed in a mixed solution of citric acid and ethylene glycol, wherein the molar ratio of La to Co to Ga to citric acid to ethylene glycol is =1:0.7:0.3:2.5: 0.53.
(6) Preparation of LaCo by dipping-high temperature roasting0.7Ga0.3O3Porous nickel catalyst: soaking the nickel material obtained in the step (4) in the cobalt-gallium perovskite precursor solution obtained in the step (5) for 12-24h at normal temperature, and then soaking at 80 deg.CoC, continuously stirring for 8 hours in a water bath, and carrying out a programmed heating process of 3 in the high-temperature roasting processoC/min is increased to 120oC, preserving the heat for 12 hours, and then 2oRaising the temperature to 650 ℃ per min, preserving the heat for 5 hours, and naturally cooling along with a muffle furnace to obtain LaCo0.7Ga0.3O3/porous nickel catalyst.
Example 2
One kind is usedCobalt-gallium catalyst for preparing low-carbon alcohol from synthetic gas, which is LaCo0.65Ga0.35O3A non-powder catalyst comprising the steps of:
(1) preparing a Ni-Al alloy block:
(a) uniformly mixing 35wt.% of 2-3 μm nickel powder and 65wt.% of 7-8 μm aluminum powder;
(b) pressing and molding under 350 MPa;
(c) sintering at high temperature in reducing atmosphere at 1350 deg.CoC, high temperature lasting for 2 hours, natural cooling,
the pressure maintaining time for press forming is 7.5 min; the reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
(2) Preliminary dealloying by chemical lye corrosion: the corrosive liquid used for primary dealloying by the corrosion of the chemical alkali liquor is 1.5M NaOH aqueous solution, the corrosion time is 20h, and the temperature is 33oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
(3) Deep dealloying by electrochemical acid corrosion: taking the nickel material obtained in the step (2) as an anode, taking a Pt sheet as a cathode and taking 0.65M HNO3The corrosion voltage is 0.4V, the corrosion time is 2.5h, and the electrochemical corrosion temperature is normal temperature.
(4) Oxidation and activation: the oxidation activation is oxidation under 40wt.% oxygen-air condition for 8 min.
(5) Preparing cobalt-gallium perovskite precursor solution: lanthanum nitrate, cobalt nitrate and gallium nitrate are sequentially mixed in a mixed solution of citric acid and ethylene glycol, wherein the molar ratio of La to Co to Ga to citric acid to ethylene glycol is =1:0.65:0.35:2.5: 0.53.
(6) Preparation of LaCo by dipping-high temperature roasting0.65Ga0.35O3Porous nickel catalyst: soaking the nickel material obtained in the step (4) in the cobalt-gallium perovskite precursor solution obtained in the step (5) for 20h at normal temperature, and then soaking at 80 deg.CoC, continuously stirring for 8 hours in a water bath, and carrying out a programmed heating process of 3 in the high-temperature roasting processoC/min is increased to 120oC, preserving the heat for 12 hours, and then 2oRaising the temperature to 650 ℃ per min, preserving the heat for 6 hours, and naturally cooling along with a muffle furnace to obtain LaCo0.65 Ga 0.35O3Porous nickel catalyst, named S.
Example 3
A Co-Ga catalyst for preparing low-carbon alcohol from synthetic gas is LaCo0.55Ga0.45O3A non-powder catalyst comprising the steps of:
(1) preparing a Ni-Al alloy block:
(a) uniformly mixing 40wt.% of 2-3 μm nickel powder and 60wt.% of 7-8 μm aluminum powder;
(b) pressing and molding under 400 Mpa;
(c) sintering at high temperature of 1400 deg.C in inert atmosphereoC, high temperature lasting for 3 hours, natural cooling,
the pressure maintaining time for press forming is 10 min; the inert atmosphere is N2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
(2) Preliminary dealloying by chemical lye corrosion: the corrosive liquid used for primary dealloying by the corrosion of the chemical alkali liquor is 2M NaOH aqueous solution, the corrosion time is 24h, and the temperature is 35oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
(3) Deep dealloying by electrochemical acid corrosion: taking the nickel material obtained in the step (2) as an anode, taking a Pt sheet as a cathode and taking 0.7M HNO3The corrosion voltage is 0.5V, the corrosion time is 3h, and the electrochemical corrosion temperature is normal temperature.
(4) Oxidation and activation: the oxidation activation is oxidation for 10min under 40wt.% oxygen-air condition.
(5) Preparing cobalt-gallium perovskite precursor solution: lanthanum nitrate, cobalt nitrate and gallium nitrate are sequentially mixed in a mixed solution of citric acid and ethylene glycol, wherein the molar ratio of La to Co to Ga to citric acid to ethylene glycol is =1:0.55 to 0.45:2.5: 0.53.
(6) Preparation of LaCo by dipping-high temperature roasting0.55Ga0.45O3Porous nickel catalyst: the impregnation is that the nickel material obtained in the step (4) is soaked in the cobalt obtained in the step (5)Soaking in the precursor solution for 24h at room temperature, and soaking at 80 deg.CoC, continuously stirring for 8 hours in a water bath, and carrying out a programmed heating process of 3 in the high-temperature roasting processoC/min is increased to 120oC, preserving the heat for 12 hours, and then 2oRaising the temperature to 650 ℃ per min, preserving the heat for 7 hours, and naturally cooling along with a muffle furnace to obtain LaCo0.55Ga0.45O3Porous nickel catalyst.
Comparative example 1
A Co-Ga catalyst for preparing low-carbon alcohol from synthetic gas is LaCo0.65Ga0.35O3A non-powder catalyst comprising the steps of:
(1) preparing a Ni-Al alloy block:
(a) uniformly mixing 35wt.% of 2-3 μm nickel powder and 65wt.% of 7-8 μm aluminum powder;
(b) pressing and molding under 350 MPa;
(c) sintering at high temperature in reducing atmosphere at 1350 deg.CoC, high temperature lasting for 2 hours, natural cooling,
the pressure maintaining time for press forming is 7.5 min; the reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
(2) Dealloying by electrochemical acid etching: taking the nickel-aluminum alloy material as an anode, taking a Pt sheet as a cathode and taking 0.65M HNO3The corrosion voltage is 0.4V, the corrosion time is 2.5h, and the electrochemical corrosion temperature is normal temperature.
(3) Dealloying by chemical lye corrosion: the corrosive liquid used for dealloying by the corrosion of the chemical alkali liquor is 1.5M NaOH aqueous solution, the corrosion time is 20h, and the temperature is 33oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
(4) Oxidation and activation: the oxidation activation is oxidation under 40wt.% oxygen-air condition for 8 min.
(5) Preparing cobalt-gallium perovskite precursor solution: lanthanum nitrate, cobalt nitrate and gallium nitrate are sequentially mixed in a mixed solution of citric acid and ethylene glycol, wherein the molar ratio of La to Co to Ga to citric acid to ethylene glycol is =1:0.65:0.35:2.5: 0.53.
(6) Preparation of LaCo by dipping-high temperature roasting0.65Ga0.35O3Porous nickel catalyst: soaking the nickel material obtained in the step (4) in the cobalt-gallium perovskite precursor solution obtained in the step (5) for 20h at normal temperature, and then soaking at 80 deg.CoC, continuously stirring for 8 hours in a water bath, and carrying out a programmed heating process of 3 in the high-temperature roasting processoC/min is increased to 120oC, preserving the heat for 12 hours, and then 2oRaising the temperature to 650 ℃ per min, preserving the heat for 6 hours, and naturally cooling along with a muffle furnace to obtain LaCo0.65Ga0.35O3Porous nickel catalyst, named D-1.
Comparative example 2
A Co-Ga catalyst for preparing low-carbon alcohol from synthetic gas is LaCo0.65Ga0.35O3A non-powder catalyst comprising the steps of:
(1) preparing a Ni-Al alloy block:
(a) uniformly mixing 35wt.% of 2-3 μm nickel powder and 65wt.% of 7-8 μm aluminum powder;
(b) pressing and molding under 350 MPa;
(c) sintering at high temperature in reducing atmosphere at 1350 deg.CoC, high temperature lasting for 2 hours, natural cooling,
the pressure maintaining time for press forming is 7.5 min; the reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
(2) Preliminary dealloying by chemical lye corrosion: the corrosive liquid used for primary dealloying by the corrosion of the chemical alkali liquor is 1.5M NaOH aqueous solution, the corrosion time is 20h, and the temperature is 33oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
(3) Deep dealloying by electrochemical acid corrosion: taking the nickel material obtained in the step (2) as an anode, taking a Pt sheet as a cathode and taking 0.65M HNO3The corrosion voltage is 0.4V, the corrosion time is 2.5h, and the electrochemical corrosion temperature is normal temperature.
(4) Preparing cobalt-gallium perovskite precursor solution: lanthanum nitrate, cobalt nitrate and gallium nitrate are sequentially mixed in a mixed solution of citric acid and ethylene glycol, wherein the molar ratio of La to Co to Ga to citric acid to ethylene glycol is =1:0.65:0.35:2.5: 0.53.
(5) Preparation of LaCo by dipping-high temperature roasting0.65Ga0.35O3Porous nickel catalyst: soaking the nickel material obtained in the step (3) in the cobalt-gallium perovskite precursor solution obtained in the step (4) for 20h at normal temperature, and then soaking at 80 deg.CoC, continuously stirring for 8 hours in a water bath, and carrying out a programmed heating process of 3 in the high-temperature roasting processoC/min is increased to 120oC, preserving the heat for 12 hours, and then 2oRaising the temperature to 650 ℃ per min, preserving the heat for 6 hours, and naturally cooling along with a muffle furnace to obtain LaCo0.65Ga0.35O3Porous nickel catalyst, named D-2.
Comparative example 3
Cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas
(1) Commercially available nickel foam was purchased and subjected to a cleaning degreasing treatment.
(2) Oxidation and activation: the oxidation activation is oxidation under 40wt.% oxygen-air condition for 8 min.
(3) Preparing cobalt-gallium perovskite precursor solution: lanthanum nitrate, cobalt nitrate and gallium nitrate are sequentially mixed in a mixed solution of citric acid and ethylene glycol, wherein the molar ratio of La to Co to Ga to citric acid to ethylene glycol is =1:0.65:0.35:2.5: 0.53.
(4) Preparation of LaCo by dipping-high temperature roasting0.65Ga0.35O3Porous nickel catalyst: soaking the nickel material obtained in the step (2) in the cobalt-gallium perovskite precursor solution obtained in the step (3) for 20h at normal temperature, and then soaking at 80 deg.CoC, continuously stirring for 8 hours in a water bath, and carrying out a programmed heating process of 3 in the high-temperature roasting processoC/min is increased to 120oC, preserving the heat for 12 hours, and then 2oRaising the temperature to 650 ℃ per min, preserving the heat for 6 hours, and naturally cooling along with a muffle furnace to obtain LaCo0.65Ga0.35O3A nickel foam catalyst, named D-3.
Before the reaction takes place, the LaCo1-αGaαO3Before the use of the porous nickel catalyst,over 3-5vol.% H2/N2Reducing for 3-5h at the reduction temperature of 700-900 ℃, and then cooling to room temperature, wherein the reaction conditions are as follows: pressure: 4Mpa, space velocity: 6000 mLgcat -1h-1
Gas composition of H2/CO/N2= 8/4/1, test condition 350oC。
TABLE 1
From Table 1, it can be seen that the S catalyst has the best selectivity for lower alcohols, the CO conversion rate is 14.9%, the total alcohol selectivity is 43.7%, the selectivity for lower alcohols and the mass fraction ratio of lower alcohols in the alcohol product are both the best, wherein the S catalyst and the D-2 catalyst have similar catalytic performances, and stability tests are performed on the S catalyst and the D-2 catalyst at 350 ℃, 4MPa and 6000 mLg at the space velocitycat -1h-1Under the condition, the S catalyst can efficiently catalyze and stabilize for 15 days, while the D-2 catalyst obviously reduces the catalytic property of the low-carbon alcohol within about 2 days, and the selectivity of the low-carbon alcohol is obviously reduced, which is related to the stripping of active components of the catalyst and a carrier at high temperature and high airspeed.
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (10)
1. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas is characterized by being LaCo1-αGaαO3Porous nickel, the alpha ranges from 0.3 to 0.45, the catalyst is a non-powder catalyst, wherein the pore size distribution of the porous nickel is between 5 and 30 mu m, and the specific surface area is between 30 and 60m2(ii)/g, porosity 50-70%, said LaCo1-αGaαO3The perovskite is uniformly loaded on the inner surfaces of the pore channels of the porous nickel, and the specific surface area of the catalyst is 20-50m2The compressive strength of the catalyst is 2-4 MPa.
2. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, which is prepared by the following steps:
(1) preparing a Ni-Al alloy body;
(2) preliminary dealloying by chemical lye corrosion;
(3) deep dealloying by electrochemical acid corrosion;
(4) oxidation activation;
(5) preparing cobalt-gallium perovskite precursor solution;
(6) preparation of LaCo by dipping-high temperature roasting1-αGaαO3Porous nickel catalyst.
3. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the Ni-Al alloy body prepared in step (1) is prepared by the following steps: (a) uniformly mixing 30-40wt.% of 1-5 mu m nickel powder and 60-70wt.% of 5-10 mu m aluminum powder, pressing and forming at 300-400Mpa, and sintering at 1300-1400 deg.C in inert atmosphere or reducing atmosphereoC, high-temperature lasting for 1-3h, naturally cooling, and keeping the pressure for the compression molding for 5-10 min; the inert atmosphere is N2The reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
4. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas as claimed in claim 1, wherein the etching solution used in the step (2) for preliminary dealloying by chemical alkaline etching is 1-2M NaOH aqueous solution, the etching time is 12-24h, and the temperature is 30-35%oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
5. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein step (3) is carried out by electrochemical acid corrosionIn the electrochemical corrosion process in the etching depth dealloying, the nickel material obtained in the step (2) is used as an anode, the Pt sheet is used as a cathode, and 0.6-0.7M HNO is used3The corrosion voltage is 0.3-0.5V, the corrosion time is 2-3h, and the electrochemical corrosion temperature is normal temperature.
6. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the oxidation activation in step (4) is oxidation under 40wt.% oxygen-air condition for 5-10 min.
7. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the cobalt-gallium perovskite precursor solution prepared in step (5): and mixing lanthanum nitrate, cobalt nitrate and gallium nitrate into the mixed solution of citric acid and glycol according to the formula, wherein the molar ratio of La to Co to Ga to citric acid to glycol: 1:(0.55-0.7):(0.3-0.45):2.5:0.53.
8. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the step (6) of impregnating and high-temperature roasting for preparing LaCo1-αGaαO3Soaking the nickel material obtained in the step (4) in the cobalt-gallium perovskite precursor solution obtained in the step (5) for 12-24h at normal temperature, and then soaking at 80 deg.CoC, continuously stirring in the water bath kettle for 8 hours.
9. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the step (7) of impregnating and high-temperature roasting for preparing LaCo1-αGaαO3Porous nickel catalyst, wherein the temperature programming process of the high-temperature calcination process is 3oC/min is increased to 120oC, preserving the heat for 24 hours, and then 2oC/min is increased to 650oAnd C, preserving the heat for 5-7 hours, and naturally cooling along with the muffle furnace.
10. The cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the cobalt-gallium catalyst is prepared from cobalt, gallium, and oxygenSaid LaCo1-αGaαO3Porous nickel catalyst was passed through 3-5vol.% H before use2/N2Reducing for 3-5h at 700-900 ℃.
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