CN101076492A - 用于制备合成气和富氢气体混合物的纳米结构金属催化剂的用途 - Google Patents
用于制备合成气和富氢气体混合物的纳米结构金属催化剂的用途 Download PDFInfo
- Publication number
- CN101076492A CN101076492A CNA2005800367787A CN200580036778A CN101076492A CN 101076492 A CN101076492 A CN 101076492A CN A2005800367787 A CNA2005800367787 A CN A2005800367787A CN 200580036778 A CN200580036778 A CN 200580036778A CN 101076492 A CN101076492 A CN 101076492A
- Authority
- CN
- China
- Prior art keywords
- metal
- purposes according
- alcohol
- hydrogen
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000008246 gaseous mixture Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- -1 3,5 disubstituted phenol Chemical class 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 5
- 239000002923 metal particle Substances 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000007789 gas Substances 0.000 claims description 45
- 238000002360 preparation method Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000010458 rotten stone Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- 238000002407 reforming Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical class C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000629 steam reforming Methods 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 238000002453 autothermal reforming Methods 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000000969 carrier Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 11
- 229960001755 resorcinol Drugs 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000725 suspension Substances 0.000 description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 229910003310 Ni-Al Inorganic materials 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002525 ultrasonication Methods 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 230000006837 decompression Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000006057 reforming reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910002440 Co–Ni Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000006140 methanolysis reaction Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 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
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
这里描述一种用于制备合成气和富氢气体混合物的纳米结构金属催化剂的用途;所述催化剂由纳米结构金属粒子组成,所述粒子通过由金属盐形成的金属络合物和模板聚合物的还原反应获得,分子量范围是1.000-50.000g mol-1的所述模板聚合物通过苯酚或3,5双取代苯酚取代的4-{1-[(苯基-2,4-双取代的)-亚肼基-烷基}-苯-1,3-二醇和甲醛或多聚甲醛在有酸或碱催化剂存在的水/醇混合物中在温度20-150℃下缩合而成。
Description
技术领域:
本发明涉及生产合成气或富氢气体混合物领域,特别是通过例如烃和醇的重整或醇的分解,用于制备这些气体或气体混合物的纳米结构金属催化剂的用途(稍后介绍)。
背景技术:
通常通过有机化合物(烃和醇被最常使用)的催化重整反应制备氢和合成气。为了制备包含氢的气体混合物,与O2的部分氧化反应,蒸汽重整或自热重整可以被应用。否则使用甲醇分解被。
从烃中制备合成气是一种人们熟知和成熟的工艺,然而在这些气体的新应用中,例如燃料电池的原料气,需要发展比目前使用的更有效率的催化系统,以便降低工作温度。为了这个原因,通常负载在氧化物材料上的Ni基催化剂或贵金属基催化剂(最多为Pt和Rh)被广泛研究。
制备富氢气体混合物中使用乙醇作为原料的优点是使用可再生资源:乙醇是生物材料发酵的自然产物。仅限于环境的考虑,可再生资源的利用意味着相对进步,因为其使得自然碳循环闭合。一种利用蒸汽重整处理从生物材料发酵获得的乙醇而产生氢和电的方法最近已有描述。甲醇的重整反应一般是通过存在多种作为载体或促进剂的材料(例如,ZnO,AL2O3,ZrO2,CeO2,Ni,Co)的Cu基催化剂进行的。另外,这些催化剂还可以通过负载在氧化物材料上的金属催化剂(例如Ni,Co或例如Rh的贵金属)获得,此方法已长时间研究并在一些专利中有描述。
甲醇的分解一般是通过带有几种载体/促进剂的Cu基催化剂或Pb基材料进行。
重整反应的催化剂一般通过两种方法准备的:
通过由金属盐或金属化合物浸渍预制的载体,再对所得产物煅烧以将前体分解成活性相,并且最终通过还原反应获得,或
通过对前体和载体材料的共沉以得到活性金属相,所得产物被煅烧和最终还原。
第二种选择经常被称为“固相结晶”,已经被用于甲醇和乙醇重整催化剂的制备(见F.Basile et al.J.Catal.2003,217,245)。
就烃和醇重整反应而言,许多反应中双金属相的存在(合金形式为佳)促进合成气和富氢气体混合物的形成这一现象已被注意到(J.P.Shenet al.Catal.Today 2002,77,89)。通过使用合金,有可能改变催化剂特性的来抑制那些不希望获得的反应(其中包括催化剂的钝化,例如在Ni基催化剂的形成焦炭)也已被关注(F.Besenbacher et al.Science 1998,279,1913)。
通常用于醇重整反应的催化剂包含高百分比活性相,以便于达到使用他们所需的性能。所有这些使得限制他们的大范围使用和扩展。因为实际中,高百分比活性相使催化剂非常昂贵,特别是当包含贵金属时。
另外,为了最大限度地选择性制备富氢气体混合物和抑制惰性反应,获得纳米结构活性金属相变的极其重要。已被证明在乙醇的蒸汽反应中制备氢时,当Co基催化剂晶体尺寸越小越有利于催化(F.Haga et al.React.Kin.Catal.Lett.1998,63,253)。保持这种纳米结构对于发展高效和长效重整催化剂非常重要,因为他们是在相对高温下工作。前述引用的“固相结晶”法已经达到了好结果(见例如F.Basile et al.J.Catal.2003,217,245)。作为另一种选择,通过微乳剂介导的溶胶-凝胶技术制备稳定的重整催化剂已被报道(J.Schicks et al.Cat.Today 2003,81,287)。但是所有这些例子显示共同的缺点,即需要大量贵金属(Rh或Pt),因此这些使他们的使用不具有优势。
在国际专利申请(公告号:WO2004/036674)中描述了模板聚合物,聚合物通过由苯酚或3,5双取代苯酚取代的4-{1-[(苯基-2,4-双取代的)-亚肼基-烷基}-苯-1,3-二醇和甲醛或多聚甲醛的缩合制备,并且能够调整不含铂的金属盐(优选含有Fe,Co和/或Ni的盐或化合物)以提供其加合物,一旦由气态氢或其它还原剂被原或在温度高于500℃惰性气氛下热解,制备适用于燃料电池的催化材料,此燃料电池以氢或其它含有氢原子的化合物(例如醇(甲醇,乙醇,乙二醇)、醛、肼甚至烃)为燃料。
进一步的研究表明这些催化材料包含的金属粒子(无论由多少金属组成)都非常小,其大小在3-50(10-10m)之间。
由高分散亚纳米或纳米粒子(10-9m)形成的催化剂已在意大利专利申请No.FI20040000154中介绍,其中特别描述了通过国际专利申请(公告号:WO2004/036674)的模板聚合物制备包含其它过渡金属的Pb或Pt基催化剂,用于制备用于氢或包含氢原子化合物燃料电池正负电极。
发明内容:
本发明发现国际专利申请(公告号:WO2004/036674)已公开的催化剂能用于制备合成气和富氢气体混合物,并带来巨大的效益。因此本发明的目的是在制备合成气和富氢气体混合物过程中使用纳米结构金属催化剂:这些催化剂从金属络合物和模板聚合物中制备,模板聚合物的分子量为1000-50000g mol-1,并且通过苯酚或3,5双取代苯酚取代的4-{1-[(苯基-2,4-双取代的)-亚肼基-烷基}-苯-1,3-二醇(4-{1-[(phenyl-2,4-disubstituted)-hydrazono-alkyl}-benzene-1,3-diol)和甲醛或多聚甲醛在有酸或碱催化剂的水/醇混合物中在温度20-150℃时的缩合制备。
本发明的另一目的是制备合成气和富氢气体混合物的工艺,其通过以下反应之一:醇分解,醇或烃的部分氧化,烃和醇的蒸汽重整和自热重整;在此工艺中,反应发生在上述提及的催化剂存在下,且温度在150-800℃之间,相对于载体其重量在0.1-10%,并且空间速度为10.000-800.000ml g-1 h-1之间。本发明的特征和优点将在下面介绍中说明。
附图说明:
图1显示随温度变化甲醇通过如例8所述的Fe,Co,Ni三金属催化剂催化分解成合成气的过程中,甲醇转化成H2,CO,CO2和CH4的百分比和这些气体产量。
图2显示随温度变化甲醇通过如例9所述的Fe,Co,Ni三金属催化剂催化分解成合成气的过程中,甲醇转化成H2,CO,CO2和CH4的百分比和这些气体产量。
图3随温度变化乙醇通过如例10所述的Fe-Co-Ni三金属催化剂催化蒸汽重整成合成气的过程中,甲醇转化成H2,CO,CO2和CH4的百分比和这些气体产量。
图4随温度变化甲烷通过如例11所述的Fe-Co-Ni催化剂催化部分氧化成合成气的过程中,甲烷转化成H2,CO,CO2和CH4的百分比和这些气体产量。
图5显示随温度变化甲烷通过如例12所述的Rh基催化剂催化甲醇的部分氧化制备合成气的过程中,甲烷转化成H2,CO,CO2和CH4的百分比和这些气体产量。
具体实施方式:
本发明的催化剂由金属盐形成的金属络合物(优选自Ni,Co,Fe,Ru,Rh,Pt,Pb,Mo,Ir,Cu,Sn和他们的二元,三元或四元组合物)和模板聚合物(已在专利申请WO2004/036674中说明)构成,其分子量为1000-50000g mol-1,并且通过苯酚或3,5双取代苯酚取代的4-{1-[(苯基-2,4-双取代的)-亚肼基-烷基}-苯-1,3-二醇和甲醛或多聚甲醛在有酸或碱催化剂的水/醇混合物中在温度20-150℃时的缩合制备。
4-{1-[(苯基-2,4-双取代的)-亚肼基-烷基}-苯-1,3-二醇优选为具有下述通式(A)的化合物:
其中R1选H和包含1-10个碳原子的碳氢根,可含有卤素原子;R2和R3(相同或不同)为H或选自卤化物、硝基、酰基、酯、羧酸、甲酰、腈、磺酸、芳基或含1-15个碳原子的直链烷基或支链烷基,并最终由卤素原子官能化或彼此相互缩合形成一个或多于一个带有苯环的缩聚环。
术语“苯酚”或“3,5双取代苯酚”优选表示带有下面通式(B)的化合物:
其中R4和R5(相同或不同)为H或选自包含OH、醚、胺、芳基和含1-15个碳原子直链或支链烷基。
本发明所述的聚合物能用具有以下结构式(C)的重复单元表示:
其中y在2-120之间,x在1-2之间,n在1-3之间,并且R1,R2,R3,R4,R5如前文所定义。
本发明的“金属盐”是选自羧酸盐、卤化物、类卤化物、醇化物、乙酰丙酮化物、甲酸盐、草酸盐、丙二酸、有机盐类似物和他们的混合物或碳酸盐、氧化物、重碳酸盐或其混合物。
通过重整烃和醇以制备本发明描述的用于制备合成气的催化剂的方法1、2、3在下文介绍,他们能够无分轩轾地工作。
方法1:
盐或金属化合物(优选自前文提及的)溶解于水,溶液被加入到含有前文已定义并由专利WO2004/036674所描述的模板聚合物(简称为聚合物)的水悬浮液。通过加入适量的1M NaOH溶液使得上述混合物为PH 8-9,接着在环境温度下剧烈搅拌10-15个小时。通过这种方法获得的固体产品(称为单金属化聚合物)被过滤、水洗涤和干燥。在丙酮或其他有机溶液中,干燥固体加入到被适当激活的多孔金属氧化物(例如硅土、矾土或二氧化铈)悬浮液中,。
在搅拌几小时后,产品经现有技术还原剂(例如NaBH4或NH2NH2)处理、过滤、水洗、干燥。
可替换的,从单金属化聚合物与多孔金属氧化物(优选硅土、矾土、二氧化铈、氧化锆或他们的混合物)反应中获得的固体产品减压蒸发分离,之后在氢气流中以300-800℃加热。
方法2:
两种盐或金属化合物(优选自前文提及的)溶解于水,溶液被加入到含有聚合物的水悬浮液。通过加入适量的1M NaOH溶液使得上述混合物的PH 8-9,接着在环境温度下剧烈搅拌10-15个小时。通过这种方法获得的固体产品(称为双金属化聚合物)经过滤、水洗和干燥。在丙酮或其他有机溶液中,干燥固体加入到被适当激活的多孔金属氧化物(例如硅土、矾土(氧化铝)或二氧化铈)悬浊液中。在搅拌几个小时后,添加过量现有技术的还原剂(例如NaBH4或NH2NH2)。固体产品经过滤、洗涤和干燥。
可替换的,从与多孔金属氧化物(优选硅土、矾土、二氧化铈、氧化锆或他们的混合物)与双金属化聚合物(优选选自含有前文提及的金属中的两种Fe、Co和Ni,或Cu、Co和Ni)反应中获得的固体产品减压蒸发分离,之后在氢气流中以300-800℃加热。
方法3:
三种金属盐或金属化合物(优选自那些前文提及的)溶解于水,上述合成溶液被加入到含有聚合物的水悬浮液。通过加入适量的1M NaOH溶液上述混合物的PH变为8-9,接着在环境温度下剧烈搅拌10-15个小时。通过这种方法获得的固体产品(三金属化聚合物)经过滤、水洗涤和干燥制备。在丙酮或其他有机溶液中,上述固体被加入到被适当激活的多孔金属氧化物(例如硅土、矾土或二氧化铈)悬浊液中,接着产品经现有技术的还原剂(例如,NaBH4或NH2NH2)处理。所得固体产品再经过滤、洗涤、干燥备。可替换的,从多孔金属氧化物(优选硅土、矾土、二氧化铈、氧化锆或他们的混合物)与三金属化聚合物反应中获得的固体产品通过减压蒸发分离,之后在氢气流中以300-800℃加热。上述三金属化聚合物在前文提及的金属中优选地包括两种选自Fe、Co和Ni,或Cu、Co和Ni。相似的方式接着能制备带有三种金属且负载在同一种材料上的催化剂。
根据本发明的一个特别优选实施例,经上述方法制备的催化剂由Fe、Co和Ni,或Cu、Co和Ni三金属组合构成,上述三金属按不同化学计量比分配,且优选具有相同原子百分比,或者上述催化剂能仅由负载在多空金属氧化物(优选Al2O3)上的Rh组成。它们能够促进通过烃或醇的重整反应(部分氧化,蒸汽重整或者自热重整)或甲醇分解的方法制备合成气或富氢气体混合物。相对于通常用于制备富氢气体混合物的催化剂,下列优点可以达到:
使用低金属容量的催化剂(其重量为所用金属载体的0.5-3%)
使用非贵金属和低价格金属
有机会在被选金属间设计和发展精准化学计量比的多金属催化剂。
在这些优点的基础上,本发明允许制备用于烃和醇的重整和分解的有效催化剂,并且成本比现今使用的技术有显著的降低。
根据本发明,催化剂活性的测试是通过将反应混合物放置在催化反应床上,再被装载入U型石英反应器中,最后被置入电炉中进行的。一个热电偶被安置在催化反应床中用以测试催化反应实际温度。到反应器的传输线被加热到110℃以使液体试剂完全蒸发。传输气体可以包含O2用以研究氧化重整或“自热重整”。在催化剂活性测定之前,催化剂在纯H2(10ml/min)中370℃下被还原30分钟。反应混合物通过按选定比率注入醇和水的液体混合物来制备,选定比率是通过一种惰性气体(Ar)确定的,注入是通过使用自动抽吸注射器完成的。催化剂的量以及气体混合物流速被选定,以达到设定的空间速度(GHSV)。反应混合物在150℃时被填入反应器中。一小时后,炉温以1℃/min的速度升高到800℃。产生的气体混成物通过气相色谱分析。乙醇、CO、CO2和甲烷的数量通过与甲烷化炉(methanizer)和火焰离子检测器(FID)串联的以He作为载体的碳分子筛(Carboxen)1006 PLOT柱(30m×0.53mm ID)测定。制备的氢的数量通过与热导热导率检测器(TCD)相连的Ar作为载体的Molsieve5A柱(25m×0.53mm ID)测定。催化剂活性通过在催化剂工作温度下醇的转化量和H2、CO、CO2和CH4的产量来评估。下列例子用于说明本发明,但不破坏其一般性。
例子1
负载在Al2O3上的Rh基催化剂的制备
溶解于20ml水中的0.3g三氯化铑水合物(Aldrich)被填加到在1g聚合物/100g水的悬浮液中。通过加入50ml NaOH 1M使混合物PH值到9,并且在环境温度下剧烈搅拌12个小时。形成的深红色沉积物经过滤、水洗几遍和在减压情况下以70℃干燥,直到其重量恒定;获得1g产品,经ICP-AES分析测得其含有4.5wt%Rh。经超声波处理(sonicated)的0.25g后生成产品在200ml丙酮中的悬浊液被加入悬浊在在100ml丙酮中的2g被激活的Al2O3,并超声波处理20分钟。制备的悬浊液在环境温度下剧烈搅拌4小时。最终,冷却到0℃,再加入1.5g小块状NaBH4。生成的混合物放置在环境温度中,2个小时后,固体残留物经过滤、几次水洗(3×50ml)和在减压情况下以70℃干燥,直到其重量恒定。经ICP-AES分析测得其含有0.85wt%Rh。
例子2
负载在Al2O3上的Rh基催化剂的制备
通过氢气还原反应例子1的制备被重复生产相类似产物。在本例中,1g包含聚合物-Rh-Al2O3的固体产品被填装进石英反应器,并在氢气流中以360℃加热1小时。之后样品在N2环境下储存。
例子3
负载于Al2O3上的Fe、Co和Ni三金属基催化剂的制备
含有1.59g四水合醋酸钴(II)(Aldrich),1.59g四水和醋酸镍(II)(Aldrich)和1.17g醋酸铁(II)(Aldrich)的水溶液(150ml)被加入到在7g聚合物/200ml水的悬浊液中。混合物通过加入100ml NaOH 1M使PH值到9,并且在环境温度下剧烈搅拌15小时。形成的深红色沉积物经过滤、几遍水洗和在70℃下减压干燥,直到其重量恒定;获得8g产品,经ICP-AES分析测得重量百分比Co4.27%,Ni4.31%和Fe3.98%。超声波处理20分钟后,经超声波处理(sonicated)的0.25g后生成产品在200ml丙酮中的悬浊液被加入2g悬浮在100ml丙酮中的活性SiO2。制备的悬浊液在环境温度下剧烈搅拌4小时。最终,冷却到0℃,再加入1.8g小块状NaBH4。生成的混合物放置在环境温度中,2个小时后,固体残留物经过滤、几次水洗(3×50ml)和在减压情况下以70℃干燥,直到其重量恒定。经ICP-AES分析测得其含有重量百分比Co 0.85%、Ni0.86%、Fe0.79%。原子百分比为:Co34Ni34Fe32。
例子4
负载于Al2O3上的Fe、Co和Ni三金属基催化剂的制备
通过氢气还原反应例子3的制备被重复生产相类似产物。这本例中,1g包含聚合物-Co-Ni-Fe-Al2O3的固体产品被填装进石英反应器,并在氢气流中以360℃加热1小时。之后样品在N2环境下储存。
例子5
负载于SiO2上的Co和Ni两金属基催化剂的制备
含有1.59g四水合醋酸钴(II)(Aldrich)和1.59g四水合醋酸镍(II)(Aldrich)的水溶液(150ml)被加入到在7g聚合物/200ml水悬浊液中。混合物通过加入100ml NaOH 1M使PH值到9,并且在环境温度下剧烈搅拌15小时。形成的深红色沉积物经过滤、几遍水洗和在减压情况下以70℃干燥,直到其重量恒定;获得7.5g产品,经ICP-AES分析测得重量百分比Co4.27%和Ni4.31%。
超声波处理20分钟后,经超声波处理的0.25g后生成产品在200ml丙酮中的悬浊液被加入2g悬浮在100ml丙酮中的激活SiO2。所得悬浊液在环境温度下剧烈搅拌4小时。最终,冷却到0℃,再加入1.2g小块状NaBH4。生成的混合物放置在环境温度中,2个小时后,固体残留物经过滤、几次水洗(3×50ml)和在减压情况下以70℃干燥,直到其重量恒定。经ICP-AES分析测得其含有重量百分比Co 0.85%和Ni0.86%。原子百分比为:Co50Ni50。
例子6
负载于SiO2上的Co和Ni两金属基催化剂的制备
通过氢气还原反应例子5的制备被重复生产相类似产物。本例中,1g包含聚合物-Ni-Co-SiO2的固体产品被填装进石英反应器,并在氢气流中以360℃加热1小时。之后样品在N2环境下储存。
例子7
负载于Al2O3上的Cu、Co和Ni三金属基催化剂的制备
含有1.75g四水合醋酸钴(II)(Aldrich)、1.75g四水合醋酸镍(II)(Aldrich)和1.82g单水合醋酸酮(II)(Aldrich)的水溶液(150ml)被加到7g聚合物/200ml水悬浊液中。混合物通过加入100ml NaOH 1M使PH值到9,并且在环境温度下剧烈搅拌15小时。形成的红棕色沉积物经过滤、几遍水洗和在减压情况下以70℃干燥,直到其重量恒定;获得8g产品,经ICP-AES分析测得重量百分比Co4.27%、Ni4.31%和Cu3.78%。超声波处理20分钟后,经超声波处理的0.25g后生成产品在200ml丙酮中的悬浊液被加入到2g激活Al2O3/100ml丙酮悬浊液中。
所得悬浊液在环境温度下剧烈搅拌2小时,固体残留物经过滤、几次水洗(3×50ml)和在减压情况下以70℃干燥,直到其重量恒定。经ICP-AES分析测得其含有重量百分比为Co 0.85%、Ni0.86%和Cu0.78%。原子百分比为:Co34Ni34Cu32。
例子8
通过聚合物-Fe-Co-Ni-Al2O3三金属催化剂催化甲醇分解成合成气
本例说明由例子3方法制备的聚合物-Fe-Co-Ni-Al2O3三金属催化剂催化甲醇分解成合成气的能力。
259.5mg由例子3方法制备的聚合物-Fe-Co-Ni-Al2O3三金属催化剂被置于反应器内,并且通过H2气流在370℃还原30分钟。催化剂活性研究是通过使用包含CH3OH(2.0%)/Ar的反应混合物,其中CH3OH/Ar通过在60.3ml min-1的Ar流中注入2.0μl/min液体CH3OH制备。这些条件被选定以达到GHSV≈14000ml g-1 h-1。其结果如图1所显,其中大约在450℃ CH3OH的转化完成。在此温度下,即使存在相当多的CO2和CH4,H2和CO仍为主要产品。超过750℃,转换到合成气(H2+CO)完成。
例子9
通过聚合物-Fe-Co-Ni-Al2O3三金属催化剂催化甲醇分解成合成气
本例说明当GHSV值大于例子8所述的值时由例子3方法制备的聚合物-Fe-Co-Ni-Al2O3三金属催化剂催化甲醇分解成合成气的能力。
96.0mg由例子3方法制备的聚合物-Fe-Co-Ni-Al2O3三金属催化剂被置于反应器内,并且通过H2气流在370℃还原30分钟。催化剂活性研究是通过使用包含CH3OH(2.0%)/Ar的反应混合物,其中CH3OH(2.0%)/Ar通过注入1.5μl/min的CH3OH到44.3ml min-1的Ar流中制备。这些条件被选定以达到GHSV≈28.000ml g-1 h-1。其结果如图2所显。在这些条件下,其结果与那些例子8的图1所示结果相当。
例子10
通过聚合物-Fe-Co-Ni-Al2O3三金属催化剂催化乙醇的蒸汽重整生成合成气
本例说明由例子3方法制备的聚合物-Fe-Co-Ni-Al2O3三金属催化剂在化学计量比条件下催化乙醇的蒸汽重整反应生成合成气的能力。
46.8mg由例子3方法制备的聚合物-Fe-Co-Ni-Al2O3三金属催化剂被置于反应器内,并且通过H2气流在370℃还原30分钟。催化剂活性研究是通过使用C2H5OH(1.0%)+H2O(1.0%)/Ar混合物,其通过注入2.5μl/min的摩尔比率为1∶1的C2H5OH+H2O的液体混合物(重量比为C2H5OH 72.2%,H2O 28.8%)到77.2ml min-1的Ar流中制备。这些条件被选定以达到GHSV≈100.000ml g-1 h-1。其结果如图3所显。在这些条件下,在大约480℃乙醇的转化完成。大约在340℃H2开始形成。H2的持续制备直到温度升高到大约760℃,其产量为100%。同时,CO和CO2形成,并伴随着少量CH4形成,在大约800℃时合成气几乎为唯一产物。
例子11
通过聚合物-Fe-Co-Ni-Al2O3三金属催化剂催化甲烷的部分氧化生成合成气
本例说明由例子3方法制备的聚合物-Fe-Co-Ni-Al2O3三金属催化剂在化学计量条件下催化甲烷的部分氧化生成合成气的能力。
14.1mg由例子3方法制备的聚合物-Fe-Co-Ni-Al2O3三金属催化剂被置于反应器内,在O2流(5%)/Ar中以900℃煅烧1小时,并且通过H2气流在370℃还原30分钟。催化剂活性研究是通过使用CH4(2.0%)+O2(1.0%)/Ar混合物,其通过适量混和CH4(20%)/Ar,O2(15%)/Ar和Ar以达到100ml min-1的总流。这些条件被选定以达到GHSV≈425.000ml g-1 h-1。其结果如图4所显。在这些条件下,甲烷的转化开始于大约500℃,然而大约在800℃H2开始形成。在温度低于800℃时,唯一产物为CO2。900℃时,甲烷的最大转化为大约35%,并伴随着H2的产量接近10%。
例子12
通过聚合物-Rh-Al2O3金属催化剂催化甲烷的部分氧化生成合成气
本例说明由例子1方法制备的Rh基催化剂在化学计量条件下催化甲烷的部分氧化生成合成气的能力。
22.4mg由例子1方法制备的聚合物-Rh-Al2O3催化剂(金属装载1wt%)被置于反应器内,并且通过H2气流在370℃还原30分钟。催化剂活性研究是通过使用CH4(2.0%)+O2(1.0%)/Ar混合物,其通过适量混和CH4(20%)/Ar,O2(15%)/Ar和Ar流以达到120ml min-1的总流。这些条件被选定以达到GHSV≈320.000ml g-1 h-1。其结果如图5所显。在这些条件下,制备CO2的反应开始于大约400℃。当O2转化达到100%和甲烷转化超过25%时,作为带有CH4燃烧产生的H2O、CO2和残留的CH4重整的结果,CO和H2的制备开始。温度高于700℃,系统的反应能力为CH4转化率恒定在接近95%,并且制备合成气。
Claims (24)
1.纳米结构金属催化剂在用于制备合成气和富氢气体混合物的工艺中的用途,所述催化剂通过由金属盐组成的金属络合物和分子量为1000-50000g mol-1的模板聚合物还原反应获得,所述模板聚合物通过苯酚或3,5双取代苯酚取代的4-{1-[(苯基-2,4-双取代的)-亚肼基-烷基}-苯-1,3-二醇和甲醛或多聚甲醛在存在酸或碱催化剂的水/醇混合物中在温度20-150℃时缩合制备。
2.根据权利要求1所述的用途,其中所述制备合成气和富氢气体混合物的工艺包括醇的分解。
3.根据权利要求1所述的用途,其中所述制备合成气和富氢气体混合物的工艺包括醇的部分氧化反应、蒸汽重整反应或自热重整反应。
4.根据权利要求1所述的用途,其中所述制备合成气和富氢气体混合物的工艺包括烃的部分氧化反应、蒸汽重整反应或自热重整反应。
5.根据权利要求2或3所述的用途,其中所述醇选自乙醇和甲醇。
6.根据权利要求5所述的用途,其中所述醇为甲醇。
7.根据权利要求4所述的用途,其中所述烃为甲烷。
8.根据权利要求1-7所述的用途,其中所述纳米结构金属催化剂仅作为反应的催化剂使用,并负载于合适的载体上,或者作为重整催化剂的促进剂包括Cu和ZnO,甚至还可以包括更多载体和/或促进剂。
9.根据权利要求1所述的用途,其中所述金属选自Ni,Co,Fe,Ru,Rh,Pt,Pb,Mo,Ir,Cu,Sn以及其二元,三元或四元混合物。
10.根据权利要求9所述的用途,其中所述金属选自Rh,Fe、Co和Ni的双金属或三金属化合物,以及Cu、Co和Ni的双金属或三金属混合物。
11.根据权利要求10所述的用途,其中所述双金属或三金属混合物包括的金属具有相同原子百分比。
12.根据权利要求1所述的用途,其中所述“金属盐”是选自羧酸盐、卤化物、类卤化物、醇化物、乙酰丙酮化物、甲酸盐、草酸盐、丙二酸、类有机盐和他们的混合物或碳酸盐、氧化物、重碳酸盐或它们的混合物。
15.根据权利要求1所述的用途,其中所述模板聚合物包括以下结构式C的重复单元:
其中y在2-120之间,x在1-2之间,n在1-3之间,并且R1,R2和R3如权利要求13所定义,而R4和R5如权利要求14所定义。
16.根据权利要求1所述的用途,其中所述金属催化剂负载在多孔金属氧化物上。
17.根据权利要求16所述的用途,其中所述多孔金属氧化物选自硅土、氧化铝、二氧化铈、氧化锆、氧化镁或其混化合物。
18.根据权利要求16所述的用途,其中所述多孔金属氧化物为氧化铝。
19.根据权利要求16所述的用途,其中负载于多孔氧化物上的所述金属催化剂的金属装载量占负载的催化剂总重量的0.1-50%。
20.根据权利要求19所述的用途,其中所述金属装载量占负载的催化剂总重量的0.5-3%。
21.根据权利要求1所述的用途,其中所述金属催化剂由高分散金属粒子组成,其粒子尺寸在3-70之间。
22.一种用于制备合成气和富氢气体混合物的工艺所用反应选自醇分解,醇或烃部分氧化,醇或烃的蒸汽重整或自热重整,其中所述反应在如权利要求1所述催化剂存在下,且温度在150-800℃之间,金属装载量占载体重量的0.1-10%,空间速度在10.000-800.000ml g-1 h-1之间条件下实施。
23.根据权利要求22所述的方法,其中所述醇选自乙醇和甲醇,所述烃为甲烷。
24.根据权利要求23所述的方法,其中所述醇为甲醇。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITFI2004A000220 | 2004-10-27 | ||
IT000220A ITFI20040220A1 (it) | 2004-10-27 | 2004-10-27 | Uso di catalizzatori metallici nanostrutturati per la produzione di gas di sintesi e miscele gassose ricche di h2 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN101076492A true CN101076492A (zh) | 2007-11-21 |
Family
ID=35744946
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2005800367787A Pending CN101076492A (zh) | 2004-10-27 | 2005-09-16 | 用于制备合成气和富氢气体混合物的纳米结构金属催化剂的用途 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20070294942A1 (zh) |
EP (1) | EP1819634A1 (zh) |
JP (1) | JP2008517865A (zh) |
CN (1) | CN101076492A (zh) |
BR (1) | BRPI0518386A2 (zh) |
CA (1) | CA2584478A1 (zh) |
IT (1) | ITFI20040220A1 (zh) |
WO (1) | WO2006045673A1 (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102333590A (zh) * | 2009-02-27 | 2012-01-25 | 日立造船株式会社 | 氨分解催化剂 |
CN102470356A (zh) * | 2010-03-31 | 2012-05-23 | 日本高度纸工业株式会社 | 包括被固定的分子催化剂的杂化无机/有机高分子催化膜材料及其制备 |
CN112439416A (zh) * | 2020-10-16 | 2021-03-05 | 大连理工大学 | 一种高分散铜负载二氧化钛纳米片的制备方法及其应用 |
CN112588279A (zh) * | 2020-12-15 | 2021-04-02 | 华东理工大学 | 一种用于甲醇蒸汽重整制氢的催化剂的制备方法及其产品和应用 |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8216437B2 (en) | 2003-10-10 | 2012-07-10 | Ohio University | Electrochemical cell for oxidation of ammonia and ethanol |
US8221610B2 (en) | 2003-10-10 | 2012-07-17 | Ohio University | Electrochemical method for providing hydrogen using ammonia and ethanol |
CA2542313C (en) | 2003-10-10 | 2012-12-04 | Ohio University | Electro-catalysts for the oxidation of ammonia in alkaline media |
US8216956B2 (en) | 2003-10-10 | 2012-07-10 | Ohio University | Layered electrocatalyst for oxidation of ammonia and ethanol |
CN100525965C (zh) * | 2006-05-26 | 2009-08-12 | 中国科学院兰州化学物理研究所 | 铜镍双金属纳米颗粒的制备方法 |
ITFI20070179A1 (it) * | 2007-07-31 | 2009-02-01 | Acta Spa | Catalizzatori per la produzione di gas di sintesi da reforming di alcoli comprendenti un supporto in zno e loro uso. |
JP4430698B2 (ja) | 2007-08-31 | 2010-03-10 | トヨタ自動車株式会社 | ヒドラゾン化合物、錯体形成用ヒドラゾン化合物、金属錯体形成用配位子、及び高分子化合物製造用単量体 |
JP4464997B2 (ja) | 2007-08-31 | 2010-05-19 | トヨタ自動車株式会社 | ヒドラゾン化合物を用いた燃料電池用電極触媒、及びヒドラゾン高分子化合物を用いた燃料電池用電極触媒 |
ITFI20080210A1 (it) * | 2008-11-03 | 2010-05-04 | Acta Spa | Catalizzatori a base di metalli non nobili per la decomposizione dell'ammoniaca e loro preparazione |
JP5494910B2 (ja) * | 2009-02-12 | 2014-05-21 | 日産自動車株式会社 | 水素生成触媒及びその製造方法 |
JP2010194519A (ja) * | 2009-02-27 | 2010-09-09 | Hitachi Zosen Corp | アンモニア分解触媒 |
JP2010194518A (ja) * | 2009-02-27 | 2010-09-09 | Hitachi Zosen Corp | アンモニア分解触媒 |
JP5546777B2 (ja) * | 2009-02-27 | 2014-07-09 | トヨタ自動車株式会社 | ヒドラゾンポリマー及び金属錯体形成用ヒドラゾンポリマー |
JP2010194517A (ja) * | 2009-02-27 | 2010-09-09 | Hitachi Zosen Corp | アンモニア分解触媒 |
JP2010194516A (ja) * | 2009-02-27 | 2010-09-09 | Hitachi Zosen Corp | アンモニア分解触媒 |
US9174199B2 (en) | 2009-05-26 | 2015-11-03 | Basf Corporation | Methanol steam reforming catalysts |
US20140295518A1 (en) * | 2011-09-30 | 2014-10-02 | Council Of Scientific & Industrial Research | Process for generation of hydrogen and syngas |
US20190330059A1 (en) * | 2016-06-28 | 2019-10-31 | King Abdullah University Of Science And Technology | Boron-containing catalysts for dry reforming of methane to synthesis gas |
CN113522265A (zh) * | 2021-07-28 | 2021-10-22 | 中国科学院兰州化学物理研究所 | 一种金属氧化物掺杂氧化铈的催化剂及其制备方法和应用 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4311582A (en) * | 1980-10-02 | 1982-01-19 | Atlantic Richfield Company | Stabilized reforming catalyst |
DE3618840A1 (de) * | 1986-06-04 | 1987-12-10 | Basf Ag | Methanol/luft-brennstoffzellen |
US5240893A (en) * | 1992-06-05 | 1993-08-31 | General Motors Corporation | Method of preparing metal-heterocarbon-nitrogen catalyst for electrochemical cells |
DE19917152A1 (de) * | 1999-04-16 | 2000-10-19 | Karlsruhe Forschzent | Dispersion und Verfahren zur Herstellung einer katalytisch wirksamen Schicht |
JP2001259426A (ja) * | 2000-03-21 | 2001-09-25 | Toyota Motor Corp | 炭化水素系燃料の改質触媒およびその製造方法並びにモノリス触媒 |
US6686308B2 (en) * | 2001-12-03 | 2004-02-03 | 3M Innovative Properties Company | Supported nanoparticle catalyst |
JP2003282078A (ja) * | 2002-03-27 | 2003-10-03 | Sony Corp | 触媒粒子及びその製造方法、ガス拡散性電極体、並びに電気化学デバイス |
AU2003301461B2 (en) * | 2002-10-21 | 2008-06-26 | Idea Lab S.R.L. | Platinum-free electrocatalyst materials |
US8227046B2 (en) * | 2002-11-29 | 2012-07-24 | Council Of Scientific And Industrial Research | Process for preparing self-assembling nanobinary and ternary oxy/hydroxides |
WO2004083116A1 (en) * | 2003-03-17 | 2004-09-30 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | CU-CUO/Zr02 CATALYST IN STEAM REFORMING OF METHANOL |
-
2004
- 2004-10-27 IT IT000220A patent/ITFI20040220A1/it unknown
-
2005
- 2005-09-16 CA CA002584478A patent/CA2584478A1/en not_active Abandoned
- 2005-09-16 JP JP2007538372A patent/JP2008517865A/ja active Pending
- 2005-09-16 CN CNA2005800367787A patent/CN101076492A/zh active Pending
- 2005-09-16 WO PCT/EP2005/054619 patent/WO2006045673A1/en active Application Filing
- 2005-09-16 EP EP05808092A patent/EP1819634A1/en not_active Withdrawn
- 2005-09-16 BR BRPI0518386-3A patent/BRPI0518386A2/pt not_active IP Right Cessation
- 2005-09-16 US US11/666,588 patent/US20070294942A1/en not_active Abandoned
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102333590A (zh) * | 2009-02-27 | 2012-01-25 | 日立造船株式会社 | 氨分解催化剂 |
CN102470356A (zh) * | 2010-03-31 | 2012-05-23 | 日本高度纸工业株式会社 | 包括被固定的分子催化剂的杂化无机/有机高分子催化膜材料及其制备 |
CN102470356B (zh) * | 2010-03-31 | 2016-08-03 | 日本高度纸工业株式会社 | 包括被固定的分子催化剂的杂化无机/有机高分子催化膜材料及其制备 |
CN112439416A (zh) * | 2020-10-16 | 2021-03-05 | 大连理工大学 | 一种高分散铜负载二氧化钛纳米片的制备方法及其应用 |
CN112588279A (zh) * | 2020-12-15 | 2021-04-02 | 华东理工大学 | 一种用于甲醇蒸汽重整制氢的催化剂的制备方法及其产品和应用 |
CN112588279B (zh) * | 2020-12-15 | 2022-08-02 | 华东理工大学 | 一种用于甲醇蒸汽重整制氢的催化剂的制备方法及其产品和应用 |
Also Published As
Publication number | Publication date |
---|---|
US20070294942A1 (en) | 2007-12-27 |
BRPI0518386A2 (pt) | 2008-11-18 |
CA2584478A1 (en) | 2006-05-04 |
ITFI20040220A1 (it) | 2005-01-27 |
EP1819634A1 (en) | 2007-08-22 |
JP2008517865A (ja) | 2008-05-29 |
WO2006045673A1 (en) | 2006-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101076492A (zh) | 用于制备合成气和富氢气体混合物的纳米结构金属催化剂的用途 | |
CN108097316B (zh) | 一种负载纳米金属颗粒的MOFs纳米材料的制备方法 | |
CN113522288B (zh) | 用于催化氨硼烷水解制氢的催化剂及其制备方法和应用 | |
CN113209976B (zh) | 一种甲醇水蒸气重整制氢用催化剂及其制备方法与应用、甲醇水蒸气重整制氢反应 | |
CN101352687A (zh) | 可用于甲烷二氧化碳干重整的催化剂、其制备方法与应用 | |
Li et al. | The role of K in tuning oxidative dehydrogenation of ethane with CO2 to be selective toward ethylene | |
CN1305567C (zh) | 一种甲醇自热重整制氢催化剂及制备方法和应用 | |
CN113042085B (zh) | 一种氮磷双掺杂石墨烯负载镍钴钯纳米催化剂的制备方法及应用 | |
CN103191744B (zh) | 一种改性蛭石负载镍催化剂及其制备方法 | |
Luo et al. | Atomic-scale observation of bimetallic Au-CuO x nanoparticles and their interfaces for activation of CO molecules | |
CN106622224A (zh) | 纳米金基催化剂在甲酸或甲酸盐合成中的应用 | |
CN113070062A (zh) | 一种催化甲酸产氢的铈基纳米球型催化剂及其制备方法 | |
Liu et al. | Effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria: Soot-ceria contact and interfacial oxygen evolution | |
Wu et al. | Engineering of the Cu+/Cu0 interface by chitosan-glucose complex for aqueous phase reforming of methanol into hydrogen | |
CN101428241A (zh) | 用于乙醇水蒸气预重整制氢的花球状催化剂及其制备方法 | |
XUE et al. | Two-dimensional gC 3N4 compositing with Ag-TiO2 as deactivation resistant photocatalyst for degradation of gaseous acetaldehyde | |
CN1640812A (zh) | 制备氢气的方法和制备氢气的装置 | |
JP5376222B2 (ja) | エタノール水蒸気改質用触媒 | |
Ashok et al. | Colloidal metal oxide nanocrystals in catalysis | |
CN110124650B (zh) | 一种石墨烯/TiO2复合物、制备方法及利用其作为催化剂催化水分解产氢的方法 | |
CN113441186A (zh) | 一种金属有机框架基三元复合材料及其制备方法 | |
CN1309692C (zh) | 富氢重组气中的co选择性甲烷化的方法 | |
CN110227455B (zh) | 一种二维层状甘油氧化纳米催化剂的制备方法 | |
CN1403195A (zh) | 镍基催化剂的制备方法 | |
CN115582124B (zh) | 一种铜基催化剂及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20071121 |