CN110787789A - 一种用于二氧化碳加氢制甲醇的催化剂的制备及其应用 - Google Patents
一种用于二氧化碳加氢制甲醇的催化剂的制备及其应用 Download PDFInfo
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- CN110787789A CN110787789A CN201911075552.8A CN201911075552A CN110787789A CN 110787789 A CN110787789 A CN 110787789A CN 201911075552 A CN201911075552 A CN 201911075552A CN 110787789 A CN110787789 A CN 110787789A
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- Prior art keywords
- catalyst
- cerium
- carrier
- carbon dioxide
- rod
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 49
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 45
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 95
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 5
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- PHSMPGGNMIPKTH-UHFFFAOYSA-K cerium(3+);trifluoromethanesulfonate Chemical compound [Ce+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PHSMPGGNMIPKTH-UHFFFAOYSA-K 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- -1 palladium metals Chemical class 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 claims 1
- 229940076286 cupric acetate Drugs 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 239000011641 cupric citrate Substances 0.000 claims 1
- 235000019855 cupric citrate Nutrition 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 36
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003245 coal Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 26
- 238000002390 rotary evaporation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 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 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910019580 Cr Zr Inorganic materials 0.000 description 1
- 229910019817 Cr—Zr Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals 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
- B01J23/70—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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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
- 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
-
- 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
- C07C29/154—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 copper, silver, gold, or compounds thereof
-
- 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
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Abstract
本发明公开了一种用于二氧化碳加氢制甲醇的催化剂的制备及其应用,属于煤化工技术领域。本发明采用棒状二氧化铈作为载体,钯、铜作为主催化剂并添加助剂。其中催化剂载体含量占催化剂重量的50%‑99.9%,活性组分含量占催化剂重量的0.1%‑50%,助剂含量占催化剂重量的0‑20%,且助剂选自K、Ca、Mg、Nb、Zn、Zr、Ag、Au、Pt、Ni、Cr、Fe、Co、Ti、La、Cd、Ga元素中的一种或两种以上。这类催化剂具有较高的活性和甲醇选择性,具有工业化应用前景。
Description
技术领域
本发明涉及一种用于二氧化碳加氢制甲醇的催化剂的制备及其应用,属于煤化工技术领域。
背景技术
二氧化碳作为一种温室气体,它的减排以及催化转化已经引起全世界的关注。其中利用太阳能等可再生能源通过光催化剂、光电催化制氢,并将其用于二氧化碳的加氢以合成甲醇等燃料是二氧化碳利用的有效途径之一。甲醇是重要的基础化工原料,通过甲醇可以制取烯烃、芳烃等大宗化学品以及汽油柴油等,也可以直接用作燃料或燃料添加剂。目前,实现二氧化碳加氢制甲醇产业化仍局限于高活性、高选择性催化剂的开发。
目前使用的二氧化碳加氢制甲醇的催化剂主要是在一氧化碳加氢制甲醇催化剂的基础上开发出来的,以Cu-Zn催化剂为主,主要选用载体包括SiO2、Al2O3、TiO2等,制备方法也大都以浸渍法或者共沉淀方法为主,但这类催化剂的催化性能不甚理想,存在CO2转化率低、甲醇选择性不高等问题。除此之外,最近还有一些新型金属氧化物催化剂的报道,比如Zr-Cd、Zr-Ga、Cr-Zn、Cr-Zr复合氧化物催化剂,这类催化剂虽然甲醇选择性比较高,可达80%,但活性不太理想。高活性、高选择性催化剂的开发仍然是目前研究的热点。
二氧化铈表面有比较丰富的氧空位,其在CO氧化、CO2制甲烷以及氯苯的催化燃烧反应中都有应用,但是利用二氧化铈催化二氧化碳加氢制甲醇的技术目前研究较少,国内鲜有报道。这可能是因为目前大部分二氧化碳制甲醇的催化剂都是来自于CO加氢制甲醇催化剂的改进,大部分都是Cu-Zn催化剂,而以二氧化铈作为载体尚有待进一步开发和研究。
发明内容
针对目前二氧化碳加氢制甲醇反应中催化活性不高、甲醇选择性低的问题,本发明提供了一种用于二氧化碳加氢制甲醇的催化剂,采用棒状二氧化铈作为载体,钯、铜作为主催化剂并添加助剂。这类催化剂具有较高的活性和甲醇选择性,具有工业化应用前景。
本发明的第一个目的是提供一种用于二氧化碳加氢制甲醇的催化剂,所述催化剂的载体为棒状的二氧化铈,活性组分为铜或者钯金属中的一种或者两种。
在一种实施方式中,所述催化剂中还需添加助剂,其中助剂为K、Ca、Mg、Nb、Zn、Zr、Ag、Au、Pt、Ni、Cr、Fe、Co、Ti、La、Cd、Ga元素中的一种或两种以上。
在一种实施方式中,所述催化剂中催化剂载体的含量占催化剂重量的50%-99.9%,活性组分的含量占催化剂重量的0.1%-50%,助剂的含量占催化剂重量的0-20%。
在一种实施方式中,所述棒状的二氧化铈,棒的长度为10-1000nm,棒的直径为2-100nm。
在一种实施方式中,所述催化剂的制备方法包括以下步骤:
(1)制备棒状二氧化铈载体:将铈的可溶性盐溶于去离子水中,并滴加氢氧化钠的水溶液,充分搅拌后进行水热反应,水热结束后,将得到的混合物离心分离得到固体并洗涤,最后干燥、焙烧,得到棒状的二氧化铈粉末;
(2)将活性组分前驱体、助剂前驱体溶于溶剂中形成溶液,然后将此溶液浸渍到步骤(1)中的棒状的二氧化铈载体上,然后进行干燥和焙烧。
在一种实施方式中,所述步骤(1)中棒状二氧化铈载体的具体制备方法为:
将铈的可溶性盐溶于去离子水中,并滴加氢氧化钠的水溶液,充分搅拌后转入水热釜进行水热反应,水热条件为90-200℃下水热反应12-72小时。水热结束后,将得到的混合物离心分离得到固体,并采用去离子水洗涤,直至洗涤液pH=7.0,最后在80℃下干燥8h并在空气氛围中焙烧,得到棒状的二氧化铈粉末。
在一种实施方式中,所述铈和氢氧化钠的摩尔比为1:100~200,焙烧温度为300~600℃,焙烧时间为2~10h。
在一种实施方式中,所述铈的可溶性盐为硝酸铈、硫酸铈铵、三氟甲磺酸铈、氯化铈、硫酸铈、碳酸铈、醋酸铈中的一种或两种以上。
在一种实施方式中,所述步骤(2)中浸渍时间为0.5~24h,焙烧温度为200~700℃,焙烧时间为1~10h。
在一种实施方式中,所述步骤(2)中助剂的前驱体为包含助剂的盐,如硝酸盐、碳酸盐、硫酸盐、醋酸盐等中的一种或两种以上。
在一种实施方式中,所述步骤(2)中活性组分的前驱体为硝酸铜、磷酸铜、硫酸铜、乙酸铜、醋酸铜、柠檬酸铜、硫氰酸亚铜、乙酰丙酮铜、氯化铜、硝酸钯、醋酸钯、乙酰丙酮钯、氯化钯中的一种或两种以上。
在一种实施方式中,所述步骤(2)中溶剂为水、乙醇、甲苯、二甲苯、乙二醇、丙酮、苯中的一种或两种以上。
本发明的第二个目的在于提供一种催化二氧化碳加氢制甲醇的方法,所述方法是利用上述催化剂。
在一种实施方式中,所述催化剂在使用之前需要经过原位还原处理:预处理气氛为H2、CO或者H2/CO的混合气,预处理温度为150~600℃,预处理时间为1~8h,预处理空速为800~30000mL/g/h。
在一种实施方式中,所述催化剂在使用之前需要经过原位还原处理:预处理气氛为H2,预处理温度为250℃,预处理时间为3h,预处理空速为12000mL/g/h。
在一种实施方式中,所述催化二氧化碳加氢制甲醇反应中,原料气为CO2/H2、CO/H2、或者CO/CO2/H2。
在一种实施方式中,所述原料气中H2/CO2的摩尔比为0.5~4。
在一种实施方式中,所述催化剂的反应条件为:反应温度为180~300℃,反应压力为1~7MPa,反应空速为800~30000mL/g/h。
在一种实施方式中,所述催化剂的反应条件为:反应温度为230℃,反应压力为5MPa,反应空速为12000mL/g/h。
在一种实施方式中,所述催化二氧化碳加氢制甲醇的反应在固定床或流化床反应器中进行。
本发明的有益效果:
(1)本发明采用棒状二氧化铈作为催化剂载体,其上负载钯、铜等作为活性组分并添加助剂,在二氧化碳加氢制甲醇的反应中具有比较高的活性以及甲醇选择性,解决了现有技术中活性和甲醇选择性不高的问题。
(2)本发明的催化剂制备方法简单,二氧化铈是一种常见的稀土材料,容易获得,具有工业化应用前景。
具体实施方式
本发明技术细节通过下述实施例做详细的说明。需要说明的是所举的实施例,其作用只是进一步说明本发明的技术特征,而不是限定本发明。同时,实施例只是给出了实现此目的的部分条件,并不意味着必须满足这些条件才可以达到此目的。
棒状二氧化铈长度、直径的测试方法:利用透射电子显微镜(TEM)或者扫描电子显微镜(SEM)观测二氧化铈的形貌、长度、直径等。
棒状二氧化铈平均长度、平均直径的计算方法:在不同位置拍得的电镜图片中,对二氧化铈的长度和直径进行统计,至少统计200个二氧化铈纳米棒,取这些纳米棒的平均长度和直径。
CO2转化率的计算公式:
甲醇选择性的计算公式:
实施例1利用不同粒径CeO2作为载体制备的催化剂及其活性测试
1)制备棒状CeO2载体:将10.416g硫酸铈溶于80mL去离子水中,并滴加氢氧化钠的水溶液(其中氢氧化钠215.2g,水500mL),充分搅拌后转入水热釜进行水热反应,110℃下水热反应18h。水热完毕后,将得到的混合物离心分离得到沉淀,并采用去离子水洗涤,直至洗涤液pH=7.0,最后在80℃下干燥8h并在空气氛围中350℃下焙烧6h,得到棒状的二氧化铈粉末,其中二氧化铈的平均长度为20nm,平均直径为6nm;
2)制备20Cu1.5Ga/CeO2(20nm,6nm)催化剂:取步骤1)所制备二氧化铈载体3.0g,将1.758g硝酸铜和0.164g硝酸镓溶于去离子水中,然后浸渍到所制备二氧化铈载体上,1h后对其进行旋转蒸发干燥,然后于350℃下焙烧3h,得到所需催化剂;
3)活性测试:在固定床反应器中对所制备催化剂进行活性评价,催化剂首先进行原位还原,还原条件如下:0.2MPa、纯H2、体积空速为12000mL/g/h、250℃原位还原3h;反应条件为:H2/CO2=3.0,温度为230℃,压力为5.0MPa,空速为12000mL/g/h,活性测试时间为10h,活性测试结果取5-10h平均值,见表1。由表1可知,此催化剂催化CO2转化率为18.2%,甲醇选择性为65.3%。
实施例2利用不同粒径CeO2作为载体制备的催化剂及其活性测试
1)制备棒状CeO2载体:将10.416g硝酸铈溶于80mL去离子水中,并滴加氢氧化钠的水溶液(其中氢氧化钠115.2g,水450mL),充分搅拌后转入水热釜进行水热反应,100℃下水热反应24h。水热结束后,将得到的混合物离心分离得到固体,并采用去离子水洗涤,直至洗涤液pH=7.0,最后在80℃下干燥8h并在空气氛围中400℃下焙烧4h,得到棒状的二氧化铈粉末,其中二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备20Cu1.5Ga/CeO2(100nm,10nm)催化剂,所用催化剂载体为步骤1)所制备的长为100nm、直径为10nm的二氧化铈,其余方法同实施例1;
3)活性测试条件同实施例1,结果见表1。由表1可知,此催化剂催化CO2转化率为17.3%,甲醇选择性为70.6%。
实施例3利用不同粒径CeO2作为载体制备的催化剂及其活性测试
1)制备棒状CeO2载体:将10.416g硝酸铈溶于80mL去离子水中,并滴加氢氧化钠的水溶液(其中氢氧化钠105.2g,水420mL),充分搅拌后转入水热釜进行水热反应,110℃下水热反应36h。水热结束后,将得到的混合物离心分离得到固体,并采用去离子水洗涤,直至洗涤液pH=7.0,最后在80℃下干燥8h并在空气氛围中500℃下焙烧6h,得到棒状的二氧化铈粉末,其中二氧化铈的平均长度为200nm,平均直径为15nm;
2)制备20Cu1.5Ga/CeO2(200nm,15nm)催化剂,所用催化剂载体为步骤1)所制备的长为200nm、直径为15nm的二氧化铈,其余方法同实施例1;
3)活性测试条件同实施例1,结果见表1。由表1可知,此催化剂催化CO2转化率为15.8%,甲醇选择性为73.2%。
实施例4改变助剂的种类
1)制备棒状CeO2载体,同实施例2,得到二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备20Cu1.5Ca/CeO2(100nm,10nm)催化剂:取步骤1)所制备二氧化铈载体3.0g,将1.758g硝酸铜和0.266g四水合硝酸钙溶于去离子水中,浸渍到所制备二氧化铈载体上,1h后对其进行旋转蒸发干燥,然后于350℃下焙烧3h,得到所需催化剂;
3)活性测试条件同实施例1,结果见表1。由表1可知,此催化剂催化CO2转化率为16.4%,甲醇选择性为71.2%。
实施例5改变助剂的种类
1)制备棒状CeO2载体,同实施例2,得到二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备20Cu1.5La/CeO2(100nm,10nm)催化剂:取步骤1)所制备二氧化铈载体3.0g,将1.758g硝酸铜和0.140g六水合硝酸镧溶于去离子水中,浸渍到所制备二氧化铈载体上,1h后对其进行旋转蒸发干燥,然后于350℃下焙烧3h,得到所需催化剂;
3)活性测试条件同实施例1,结果见表1。由表1可知,此催化剂催化CO2转化率为19.6%,甲醇选择性为73.1%。
实施例6改变活性成份的用量
1)制备棒状CeO2载体,同实施例2,得到二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备15Cu1.5Ga/CeO2(100nm,10nm)催化剂:取步骤1)所制备二氧化铈载体3.0g,将1.319g硝酸铜和0.164g硝酸镓溶于去离子水中,浸渍到所制备二氧化铈载体上,1h后对其进行旋转蒸发干燥,然后于350℃下焙烧3h,得到所需催化剂;
3)活性测试条件同实施例1,结果见表1。由表1可知,此催化剂催化CO2转化率为15.6%,甲醇选择性为72.1%。
实施例7改变原位还原时的原料气
1)制备棒状CeO2载体,同实施例2,得到二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备20Cu1.5Ga/CeO2(100nm,10nm)催化剂,同实施例2;
3)活性测试:在固定床反应器中对所制备催化剂进行活性评价,催化剂首先进行原位还原,还原条件如下:0.2MPa、CO/H2=1/3、体积空速为8000mL/g/h、300℃原位还原4h;反应条件为:H2/CO2=3.0,温度为230℃,压力为5.0MPa,空速为12000mL/g/h,活性测试时间为10h,活性测试结果取5-10h平均值,见表1。由表1可知,此催化剂催化CO2转化率为12.3%,甲醇选择性为72.6%。
实施例8改变催化反应的压力
1)制备棒状CeO2载体,同实施例2,得到二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备20Cu1.5Ga/CeO2(100nm,10nm)催化剂,同实施例2;
3)活性测试:在固定床反应器中对所制备催化剂进行活性评价,催化剂首先进行原位还原,还原条件如下:0.2MPa、纯H2、体积空速为12000mL/g/h、250℃原位还原3h;反应条件为:H2/CO2=3.0,温度为230℃,压力为3.0MPa,空速为12000mL/g/h,活性测试时间为10h,活性测试结果取5-10h平均值,见表1。由表1可知,此催化剂催化CO2转化率为13.5%,甲醇选择性为62.6%。
实施例9改变活性成份的种类
1)制备棒状CeO2载体,同实施例2,得到二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备5Pd1In/CeO2(100nm,10nm)催化剂:取步骤1)所制备二氧化铈载体3.0g,将0.326g硝酸钯和0.078g硝酸铟溶于去离子水中,浸渍到所制备二氧化铈载体上,1h后对其进行旋转蒸发干燥,然后于500℃下焙烧2h,得到所需催化剂;
3)活性测试条件同实施例1,结果见表1。由表1可知,此催化剂催化CO2转化率为12.1%,甲醇选择性为76.2%。
实施例10改变助剂的种类
1)制备棒状CeO2载体,同实施例2,得到二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备15Cu2Pd3Mg/CeO2(100nm,10nm)催化剂:取步骤1)所制备二氧化铈载体3.0g,将1.319g硝酸铜、0.130g硝酸钯和0.555g硝酸镁溶于去离子水中,浸渍到所制备二氧化铈载体上,1h后对其进行旋转蒸发干燥,然后于420℃下焙烧3h,得到所需催化剂;
3)活性测试条件同实施例1,结果见表1。由表1可知,此催化剂催化CO2转化率为17.8%,甲醇选择性为75.6%。
实施例11不添加助剂
1)制备棒状CeO2载体,同实施例2,得到二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备20Cu/CeO2(100nm,10nm)催化剂:取步骤1)所制备二氧化铈载体3.0g,将1.758g硝酸铜溶于去离子水中,浸渍到所制备二氧化铈载体上,1h后对其进行旋转蒸发干燥,然后于350℃下焙烧3h,得到所需催化剂;
3)活性测试条件同实施例1,结果见表1。由表1可知,此催化剂催化CO2转化率为12.6%,甲醇选择性为70.6%。
实施例12不添加助剂
1)制备棒状CeO2载体,同实施例2,得到二氧化铈的平均长度为100nm,平均直径为10nm;
2)制备5Pd/CeO2(100nm,10nm)催化剂:取步骤1)所制备二氧化铈载体3.0g,将0.326g硝酸钯溶于去离子水中,浸渍到所制备二氧化铈载体上,1h后对其进行旋转蒸发干燥,然后于500℃下焙烧2h,得到所需催化剂;
3)活性测试条件同实施例1,结果见表1。由表1可知,此催化剂催化CO2转化率为9.8%,甲醇选择性为65.8%。
对比例1
1)制备无特定形貌CeO2载体:将15.0g Ce(NO3)3·6H2O配成金属离子浓度为1.0mol/L的水溶液,然后加热至60℃,缓慢滴加浓度为1.0mol/L的氨水溶液,直至pH=9.0,然后保温2h。将得到的沉淀洗涤、干燥,并于马弗炉中400℃焙烧2h,得到无特定形貌CeO2载体;
2)制备20Cu1.5Ga/CeO2催化剂:所用载体为步骤1)所得无固定形貌的二氧化铈载体,其余催化剂制备过程和条件同实施例2;
3)活性测试条件同实施例2,结果见表1。由表1可知,此催化剂催化CO2转化率为5.8%,甲醇选择性为38.7%。
对比例2
1)制备无特定形貌CeO2载体,同对比例1;
2)制备5Pd1In/CeO2催化剂:所用载体为步骤1)所得无固定形貌的二氧化铈载体,其余催化剂制备过程和条件同实施例9;
3)活性测试条件同实施例9,结果见表1。由表1可知,此催化剂催化CO2转化率为3.1%,甲醇选择性为35.2%。
对比例3
1)制备无特定形貌CeO2载体,同对比例1;
2)制备20Cu/CeO2催化剂:所用载体为步骤1)所得无固定形貌的二氧化铈载体,其余催化剂制备过程和条件同实施例11;
3)活性测试条件同实施例11,结果见表1。由表1可知,此催化剂催化CO2转化率为5.2%,甲醇选择性为30.2%。
对比例4
1)制备无特定形貌CeO2载体,同对比例1;
2)制备5Pd/CeO2催化剂:所用载体为步骤1)所得无固定形貌的二氧化铈载体,其余催化剂制备过程和条件同实施例12。
3)活性测试条件同实施例12,结果见表1。由表1可知,此催化剂催化CO2转化率为2.6%,甲醇选择性为26.5%。
表1不同催化剂以及不同评价条件下二氧化碳加氢制甲醇的催化性能
从表1可以看出,采用本发明催化剂时,催化活性和甲醇选择性都有较大幅度的提升,同时助剂以及反应条件都会影响催化剂的性能。采用无特定形貌的二氧化铈为载体的催化剂,甲醇选择性一般不高于50%,而且催化剂的活性也比较低。而采用棒状二氧化铈作为载体,不但可以将转化率提升至将近20%,同时也大大提高了甲醇的选择性,且催化剂制备方法相对简单,具有工业化应用前景。
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。
Claims (10)
1.一种用于二氧化碳加氢制甲醇的催化剂,其特征在于,所述催化剂的载体为棒状的二氧化铈,活性组分为铜或者钯金属中的一种或者两种。
2.根据权利要求1所述的催化剂,其特征在于,所述催化剂中还需添加助剂,其中助剂为K、Ca、Mg、Nb、Zn、Zr、Ag、Au、Pt、Ni、Cr、Fe、Co、Ti、La、Cd、Ga元素中的一种或两种以上。
3.根据权利要求1或2所述的催化剂,其特征在于,所述催化剂中载体的含量占催化剂重量的50%-99.9%,活性组分的含量占催化剂重量的0.1%-50%,助剂的含量占催化剂重量的0-20%。
4.根据权利要求1所述的催化剂,其特征在于,所述棒状的二氧化铈,棒的长度为10-1000nm,棒的直径为2-100nm。
5.根据权利要求2所述的催化剂,其特征在于,所述催化剂的制备方法如下:
(1)制备棒状二氧化铈载体;将铈的可溶性盐溶于去离子水中,并滴加氢氧化钠的水溶液,充分搅拌后进行水热反应,水热结束后,将得到的混合物离心分离得到固体并洗涤,最后干燥、焙烧,得到棒状的二氧化铈粉末;
(2)将活性组分前驱体、助剂前驱体溶于溶剂中形成溶液,然后将此溶液浸渍到步骤(1)中的棒状的二氧化铈载体上,然后进行干燥和焙烧。
6.根据权利要求5所述的催化剂,其特征在于,步骤(1)中铈的可溶性盐为硝酸铈、硫酸铈铵、三氟甲磺酸铈、氯化铈、硫酸铈、碳酸铈、醋酸铈中的一种或两种以上;步骤(2)中助剂的前驱体为硝酸盐、碳酸盐、硫酸盐、醋酸盐等中的一种或两种以上;活性组分的前驱体为硝酸铜、磷酸铜、硫酸铜、乙酸铜、醋酸铜、柠檬酸铜、硫氰酸亚铜、乙酰丙酮铜、氯化铜、硝酸钯、醋酸钯、乙酰丙酮钯、氯化钯中的一种或两种以上。
7.一种二氧化碳加氢制甲醇的方法,其特征在于,所述方法是利用权利要求1-6任一所述的催化剂。
8.根据权利要求7所述的二氧化碳加氢制甲醇的方法,其特征在于,所述催化剂在使用之前需要经过原位还原处理:预处理气氛为H2、CO或者H2/CO的混合气,预处理温度为150~600℃,预处理时间为1~8h,预处理空速为800~30000mL/g/h。
9.根据权利要求7或8所述的二氧化碳加氢制甲醇的方法,其特征在于,所述方法的反应温度为180~300℃,反应压力为1~7MPa,反应空速为800~30000mL/g/h,反应在固定床或流化床反应器中进行。
10.根据权利要求7-9任一所述的二氧化碳加氢制甲醇的方法,其特征在于,所述方法的原料气为CO2/H2、CO/H2、或者CO/CO2/H2。
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