CN114682283B - Carbon-nitrogen coated supported metal monoatomic catalyst, preparation method and application thereof - Google Patents
Carbon-nitrogen coated supported metal monoatomic catalyst, preparation method and application thereof Download PDFInfo
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- CN114682283B CN114682283B CN202011637270.5A CN202011637270A CN114682283B CN 114682283 B CN114682283 B CN 114682283B CN 202011637270 A CN202011637270 A CN 202011637270A CN 114682283 B CN114682283 B CN 114682283B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 132
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 90
- 239000002184 metal Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000011069 regeneration method Methods 0.000 claims abstract description 4
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 74
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 238000000197 pyrolysis Methods 0.000 claims description 24
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 22
- 239000002808 molecular sieve Substances 0.000 claims description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 17
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- 238000010025 steaming Methods 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 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 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 230000000415 inactivating effect Effects 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 143
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 69
- 239000002904 solvent Substances 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 238000001704 evaporation Methods 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000001681 protective effect Effects 0.000 description 17
- 125000004429 atom Chemical group 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010948 rhodium Substances 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 241000894007 species Species 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000969 carrier Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- -1 propylene, ethylene Chemical group 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UYLXCEMJQIZPER-UHFFFAOYSA-N C(#N)N(N=O)[N+](=O)[O-] Chemical compound C(#N)N(N=O)[N+](=O)[O-] UYLXCEMJQIZPER-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- UOQASXHGTWIPDZ-UHFFFAOYSA-N chromium(3+) trinitrate trihydrate Chemical compound [N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].O.O.O.[Cr+3] UOQASXHGTWIPDZ-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- SLIOYUPLNYLSSR-UHFFFAOYSA-J tetrachloroplatinum;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl SLIOYUPLNYLSSR-UHFFFAOYSA-J 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen 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
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
-
- 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
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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
- Y02P20/584—Recycling of catalysts
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Abstract
The invention protects a novel chip with CN@M 1 A catalyst with a carrier structure, a preparation method, a regeneration method and application thereof, wherein M is noble metal and transition metal, and at least part of M metal in the catalyst is dispersed on a carrier in a single atom site state. Compared with the traditional catalyst, the catalyst has lower active metal consumption and higher catalytic conversion rate and selectivity.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to an alkane dehydrogenation catalyst.
Background
The low-carbon olefin comprises isobutene, 1-butene, 2-butene, 1, 3-butadiene, propylene, ethylene and the like, is a basic raw material for petrochemical industry, and is widely used for producing organic chemical raw materials, resin rubber plastics, synthetic gasoline and the like. A large amount of lower alkanes are produced in the petrochemical industry in the form of byproducts, and the corresponding lower olefins can be obtained by dehydrogenating the lower alkanes, so that the lower alkanes are gradually paid attention to the academia and industry.
The catalytic system for the dehydrogenation of the lower alkane, which has been successfully applied to industrialization, is mainly a supported metal nanoparticle catalytic system taking an oxide as a carrier, and active metal elements can be platinum, chromium, vanadium, molybdenum, gallium and the like, but since the eighties of the last century, the two types of platinum series and chromium series are only successfully applied to the industrialization, and a great deal of researches are only carried out on the basis of the two types of platinum series and chromium series, and a plurality of auxiliary agents such as lithium, potassium, magnesium, calcium, lanthanum, zinc, tin and the like are added for modification, so as to try to utilize the interaction of the metal elements with active components in the catalyst and the carrier to regulate and optimize the catalytic performance.
However, both types of catalysts have significant drawbacks: the platinum exists in the form of nano particles on the platinum-based catalyst, precious metals are not fully exposed on the surface of the catalyst, the loading capacity is high, and the utilization rate is low; chromium compounds have high toxicity, are easy to cause environmental pollution, have short continuous reaction time in alkane dehydrogenation reaction, and rapidly accumulate carbon on the surface of a catalyst in the reaction process, and need to frequently switch and regenerate and catalyze two processes.
The active metal exists in the form of single atom on the single atom catalyst, and the application of the active metal to the dehydrogenation reaction of lower alkane can effectively avoid the problems: firstly, the metal element has the highest atomic utilization rate when existing in a single-atom form, so that the metal consumption can be reduced, and non-toxic metal elements are selected to reduce the cost and pollution; and secondly, the monodisperse atomic active sites are single, no adjacent active sites exist, the activation of C-H bonds can be catalyzed with high selectivity without damaging the C-C bonds, the generation of byproducts is avoided, the generation of carbon deposit is effectively inhibited, and the service life of the catalyst is effectively prolonged.
Patent CN107626294a discloses a method of preparing a noble metal monoatomic catalyst using in situ synthesis to form a noble metal monoatomic catalyst on a carbon nitrogen (N-C) based support. Patent CN109225306a discloses the use of noble metal monoatomic catalysts in the dehydrogenation of lower alkanes. The preparation of the monoatomic catalysts in both patents requires a considerable preparation time, and in situ preparation requires a stirring time of 24 hours and a drying time of more than 24 hours, which greatly limits the productivity for industrial production. In addition, the catalyst disclosed in the above patent has a structure of M/N-C in most cases, although some of the catalyst has a structure of M/N-C-Al 2 O 3 But its catalytic performance is significantly lower than that of the M/N-C catalyst. In addition, in this patent, considering the mixing problem with the organic ligand, the metal precursor should be selected as much as possible from organic salts such as acetylacetonate, resulting in high production costs and difficulty in controlling the actual load of the metal. More importantly, the catalysts of the patents are all powder, and are produced in actual industryThe molded catalyst is needed in the production process, otherwise, the problems of coking, blocking and the like are easy to occur. The monoatomic catalyst of this patent is used in industry, and has the following problems: 1. a method for preparing a monoatomic catalyst rapidly and efficiently; 2. a method for rapid regeneration of a catalyst.
There is an urgent need for a shaped catalyst which meets the needs of industrial production, is simple in raw materials, simple in preparation, and can be rapidly regenerated after the catalytic performance is reduced.
Disclosure of Invention
The invention protects a novel chip with CN@M 1 Catalyst of support structure, wherein M is selected from one or more of noble metal atoms or transition metals, wherein the noble metal atoms are selected from Pt, au, ru, rh, pd, ir or Ag and the transition metals are selected from Fe, co, mn, ni or Cu, M 1 Indicating that the metal is present in a single atomic site state. Preferably the M metal is selected from Pt, ru, pd, ir, rh or Co. The M content of the catalyst is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight, based on the weight of the catalyst.
The carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silica-alumina, titanium oxide or a mixture of any two or more of the above; the catalyst carrier plays a role of loading, and the form of the carrier is selected from non-formed powder or formed structure. The molded structures include spheres, strips, cylinders, multi-void channels, honeycombs, and the like. As an example, the present invention implements alumina, molecular sieves, titania supports.
CN represents nitrogen doped carbon, also labeled C-N or N-C, or carbon nitrogen, and in the present invention, these terms are synonymous. The @ symbol means the meaning of cladding, "CN @ M 1 The carrier means CN coated on M 1 Surface of the carrier.
The catalyst further comprises Zn, wherein the Zn is derived from a precursor ZIF-8 coating of CN formed in the preparation process of the catalyst. The Zn content is from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, particularly preferably from 0.1 to 5% by weight, based on the weight of the catalyst.
The invention further provides a novel catalyst having CN@M 1 -Zn/carrier structured catalyst whereinThe M content is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight, the Zn content is from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, particularly preferably from 0.1 to 5% by weight, based on the weight of the catalyst, the M metal and the catalyst being as defined above. Preferably, the M metal is Pt, ru, pd, ir or Rh.
The invention discloses a method for quickly preparing a catalyst with CN@M 1 A method of supporting a structured monoatomic catalyst, the method comprising:
step one: the metal active component is loaded on a carrier and marked as a catalyst precursor;
step two: coating the catalyst precursor with ZIF-8;
step three: in vacuum, inert gas or H 2 Pyrolysis is carried out in the atmosphere, and the pyrolysis temperature is 400-1000 ℃.
The carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silicon dioxide-alumina, titanium oxide or a mixture of any two or more of the alumina, the molecular sieve and the titanium oxide, and the invention is exemplified by the alumina, the molecular sieve and the titanium oxide carrier; the carrier serves as a support.
In the first step, the M metal active component is supported on the carrier in a metal precursor manner, and any means known in the art may be used for supporting, including impregnation, spin evaporation, adsorption, ion exchange, incipient wetness impregnation, precipitation, spray drying, grinding, and the like, and the impregnation method and the spin evaporation method are used for supporting in the embodiment of the present invention. The M metal precursor may be an inorganic metal salt, an organic metal salt or a metal complex, preferably the metal precursor is a nitrate, chloride, sulfate, acetate, oxalate, acetylacetonate or a chlorine complex, the active metal is selected from one or more of noble metal atoms or transition metals, wherein the noble metal atoms are selected from Pt, au, ru, rh, pd, ir or Ag, and the transition metals are selected from Fe, co, mn, ni or Cu. Preferably M is Pt, ru, pd, ir, rh or Co. The M content is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight, based on the weight of the catalyst.
In the second step, the ZIF-8 material is prepared according to the prior art method or purchased commercially.
The coating process comprises the step of retaining the ZIF-8-containing suspension, emulsion or powder, etc., as uniformly as possible on the surface of the article to be coated, using existing conventional means. Methods that may be used include dipping, spin steaming, and the like. ZIF-8 and Al 2 O 3 The theoretical mass ratio of (2) is 0.005-0.50:1, the actual addition values in the embodiment of the present invention are within this range.
The inventor finds that the previously prepared ZIF-8 coated active metal-loaded catalyst carrier can avoid the problem that in the prior art (CN 109225306A), only a powder catalyst taking an N-C component as a carrier can be manufactured, and a granular catalyst can be obtained, so that the industrial production efficiency is improved, and the catalyst can be directly applied to industrial devices. Meanwhile, only active metal is loaded on the carrier, so that the raw material range of the active metal salt is enlarged, expensive acetylacetonate is avoided, and the preparation cost of the catalyst is greatly reduced. The method also solves the problem that noble metal cannot be quantitatively added in the prior art, and avoids the problem that the actual load capacity is reduced and the load cannot be quantitatively carried out due to the fact that liquid-phase active metal remains in the solid-liquid separation process in the prior art. In addition, the catalysts formed in the present invention also have a new structure different from the catalysts formed in situ in the prior art (CN 109225306 a), but also have similar catalytic activity.
Step three, pyrolysis temperatures of 450-800℃are preferred.
Further, the invention protects a CN@M 1 A method for regenerating a single-atom catalyst having a support structure, the method comprising:
step A: removal results in CN@M 1 A catalyst-poisoning or deactivating substance of the support structure to form a catalyst-containing precursor;
and (B) step (B): coating the catalyst precursor to be regenerated with ZIF-8;
step C: in vacuum, inert gas or H 2 Pyrolysis is carried out in the atmosphere, and the pyrolysis temperature is 400-1000 ℃.
Wherein, the step A can remove the inactivating substance by the conventional method, the inactivating substance comprises carbon deposit, sulfur and the like, and the removing method comprises the following steps of using O 2 Empty spaceRemoval by oxidation of gases, or by use of H 2 And (5) reduction and removal.
The carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silicon dioxide-alumina, titanium oxide or a mixture of any two or more of the alumina, the molecular sieve and the titanium oxide, and the invention is exemplified by the alumina, the molecular sieve and the titanium oxide carrier; the carrier serves as a support.
The M metal active component is supported on the carrier in the form of a metal precursor, and can be carried out by any means known in the art, including impregnation, rotary evaporation, adsorption, ion exchange, incipient wetness, precipitation, spray drying, ball milling and the like. The M metal salt is an inorganic metal salt, an organic metal salt or a complex, preferably the metal salt is a nitrate, chloride, sulfate, acetate, oxalate, acetylacetonate or a chloride complex. The active metal is selected from one or more of noble metal atoms selected from Pt, au, ru, rh, pd, ir, ag or transition metals selected from Fe, co, mn, ni or Cu, preferably M is Pt, ru, pd, ir, rh or Co. M is M 1 Indicating that the metal is present in a single atomic site state. The M content is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight, based on the weight of the catalyst.
In step C, the pyrolysis temperature is preferably 450-800 ℃.
Further, the invention protects the CN@M 1 Use of a single-atom catalyst of a support structure for catalyzing the dehydrogenation of alkanes, C, to form olefins 2-6 Alkane, dehydrogenation to obtain C 2-6 An olefin.
The invention also discloses a method for preparing lower olefin by dehydrogenating lower alkane, which comprises the following steps of using the CN@M 1 Mono-atom catalyst of carrier structure for catalyzing dehydrogenation of lower alkane to form lower alkene, wherein the alkane is C 2-6 Alkane, dehydrogenation to obtain C 2-6 An olefin.
Definition and interpretation
The term "dispersed state in a single-atom site state, single-atom distribution, single-atom morphology or single-atom level" as used herein refers to a state in which the active metal elements are separated from each other in a state in which metal atoms (ions) are independent of each other, and the active metal atoms do not form a metal-metal bond directly connected to each other, and are dispersed in an atomic scale or in a single-atom site state. The metal dispersed in the single atomic site state may exist in an atomic state or in an ionic state, and more likely is between an atomic and an ionic state (the valence state is between two valence states). In the metal state nano-particles, metal atoms in the same particle are mutually bonded, and obviously, the metal atoms do not belong to a monoatomic state or a monoatomic dispersion state defined by the invention; for compound or mixture nanoparticles formed by metal and other elements (such as O, S or even other metals), although the metal is separated by the other elements, the compound or mixture nanoparticles tend to be easily converted into metallic nanoparticles (such as oxide nanoparticles which are converted through reduction), and the compound or mixture nanoparticles also do not belong to a single-atom site state or a single-atom separation state defined by the invention. The metals in the single atomic site state protected by the present invention are theoretically completely independent of each other. However, random deviations in the control of the operating conditions of the different batch preparations do not exclude the presence of small amounts of agglomerated metal species, such as clusters containing a number of atoms or ions; nor does it exclude that part of the metal assumes a nanoparticle state. In other words, it is possible that the active metal in the catalyst of the present invention exists in a single-atom site dispersed state, while a cluster state containing aggregation of metal atoms exists partially, and/or a part of the metal exhibits a nanocrystalline state. And the monoatomic state transitions to a cluster and/or nanostate as the external environment changes. The monoatomic state as claimed in the present application requires a certain proportion of monoatomic noble metal in the different forms of monoatomic noble metal monoatoms, noble metal clusters, noble metal nanocrystals, etc., for example, above 10%, preferably above 20%, particularly preferably above 50%. But is limited to the current technical means, the method can only analyze and characterize a large number of different local areas randomly selected in a catalyst test sample through a relatively rough statistical means by a high-resolution spherical aberration electron microscope, randomly select various noble metal existence states for statistical analysis, or analyze the catalyst sample through an X-ray absorption fine structure spectrum (EXAFS) capable of characterizing the whole information of the sample, obtain the ratio of metal and other atomic bonding signals to metal-metal bonding signals, and determine the approximate ratio of monoatomic states. It is noted that essentially, the catalyst product is obtained with even a partial monoatomic state as long as the technique of the invention is used in the product, which product shows an improvement in performance. Therefore, if only the product is prepared by the method provided by the invention, the three-way catalyst with single atom characteristics is prepared, and the three-way catalyst is considered to be within the scope of protection of the application.
CN represents nitrogen doped carbon, also labeled C-N or N-C, or carbon nitrogen, and in the present invention, these terms have the same meaning.
Complexes are also referred to as complexes, including complexes of noble or transition metals with ligands, common ligands including halogens (fluorine, chlorine, bromine, iodine), nitro, nitroso, cyano, ammonia, water molecules or organic groups, and are typically chloro complexes, ammine complexes, cyano complexes, and the like, including chloroplatinic acid, chloroplatinate, chloroplatinic acid hydrate. See "handbook (essence) of noble metal Compound and Complex Synthesis" (Yu Jianmin, 2009, chemical industry Press).
The beneficial effects are that:
1. the invention obtains a catalyst with CN@M 1 New monoatomic catalysts of support structure in which the metal is present in a monoatomic grade of separation.
2. According to the invention, the active metal is directly loaded on the carrier, and the ZIF-8 is coated with the noble metal, so that the single-atom catalyst is formed by pyrolysis, and compared with the single-atom catalyst synthesis method in the prior art, the preparation time is saved, the preparation efficiency is greatly improved, the raw material cost is reduced, and the preparation method is suitable for the preparation and application of industrial catalysts. In addition, the problem of quantitative loading of active metals is solved.
3. A simple method for regenerating a monoatomic catalyst is provided.
4. The catalyst has higher catalytic alkane dehydrogenation activity.
Drawings
FIG. 1 shows the change in appearance of the alumina pellets, coated with ZIF-8 (at different levels), pyrolyzed to CN coated alumina pellets, where B1-B5 show the appearance of alumina pellets of different coating concentrations (essentially white) and C1-C5 show the appearance of alumina pyrolyzed to CN coated (C1 yellow, C2 brown, C3 dark brown, C4 black, C5 black, respectively).
FIG. 2 is an appearance of different carriers and different shaped carriers at different stages, including carriers (A1-A4) -ZIF-8 coated (B1-B4) -pyrolysis to form CN coated carriers (C1-C4). Wherein (A1) is a small spherical Al 2 O 3 White, (A2) five-tooth spherical Al 2 O 3 White, (A3) small sphere NaY molecular sieve light yellow, (A4) short rod-shaped TiO 2 White; coated (B1) globular ZIF-8@Al 2 O 3 White, (B2) five-tooth spherical ZIF-8@Al 2 O 3 White, (B3) small sphere ZIF-8@NaY molecular sieve light yellow, (B4) short rod-shaped ZIF-8@TiO 2 Pale yellow; pellets CN@Al after pyrolysis (C1) 2 O 3 Black, (C2) pentadentate sphere cn@al 2 O 3 Grey, (C3) globular CN@NaY molecular sieve black, (C4) CN@ short bar-shaped TiO 2 Grey.
FIG. 3 is a graph showing the change in appearance of catalysts before and after loading with different active metals, respectively (A) Al 2 O 3 White; after loading metal, (B1) Ir/Al is obtained 2 O 3 Pale yellow, (B2) Rh/Al 2 O 3 Yellow, (B3) Ru/Al 2 O 3 Light brown, (B4) Co/Al 2 O 3 Light pink; after coating, (C1) ZIF-8@Ir/Al is obtained 2 O 3 Pale yellow, (C2) ZIF-8@Rh/Al 2 O 3 Pale yellow; (C3) ZIF-8@Ru/Al 2 O 3 Off-white, (C4) ZIF-8@Co/Al 2 O 3 Purple powder; after pyrolysis, black (D1) CN@Ir/Al is obtained 2 O 3 ，(D2)CN@Rh/Al 2 O 3 ，(D3)CN@Ru/Al 2 O 3 ，(D4)CN@Co/Al 2 O 3 。
FIG. 4 shows the microstructure of the raw materials and products at different stages dynamically, A-C shows the surface morphology of alumina, D-F shows the crystal configuration of ZIF-8 formed on the surface of alumina after coating ZIF-8, and G-I shows the microstructure of the catalyst surface after pyrolysis.
Detailed Description
Terms and explanations used in the examples:
concentration of metal precursor: calculated by the mass of metal elements, for example, pd in 0.02g/g concentration is expressed as the content of Pd element in each gram of solution is 0.02g
Micro-reflection device: fixed bed microreactor or microreactor device
Micro-reverse tail gas: tail gas produced after reaction in microreactor or microreactor device
min: minute (min)
h: hours of
wt%: mass percent
TEM: transmission electron microscope (Transmission Electron Microscope)
HR-TEM: high resolution transmission electron microscope (High Resolution Transmission Electron Microscope)
AC-STEM: spherical aberration correction transmission electron microscope (Spherical Aberration-Corrected Scanning Transmission Electron Microscopy)
General procedure or raw materials preparation method
1. ZIF-8 preparation:
preparation of ZIF-8 methanol dispersion, 40mmol of zinc nitrate and 240mmol of 2-methylimidazole were dissolved in 400mL of methanol, respectively, and after the above raw materials were sufficiently dissolved, the 2-methylimidazole solution was added to the zinc nitrate solution, and stirred at room temperature for 24 hours to obtain a methanol dispersion of ZIF-8, which was labeled ZIF-8 (MeOH). The methanol dispersions of ZIF-8 used in the examples herein were prepared according to this method (same ratio).
2. The application test method comprises the following steps: alkane dehydrogenation experiments (propane dehydrogenation to propylene is taken as an example)
The catalytic performance of the catalyst was evaluated by using a fixed bed continuous flow reaction apparatus, 1.0g of the catalyst was loaded in an 8mm inner diameter straight quartz reaction tube, the reaction temperature was controlled at 600℃by a tube type resistance furnace, the flow rate of pure propane was controlled at 26.2mL/min by a mass flow meter, and purging was performed before and after the reaction using nitrogen or other inert gases.
Assembly of HP-PLOTAl using a gas chromatograph of Shimadzu 2 O 3 The reaction product was analyzed by S capillary chromatography column to sample after 5 minutes of reaction gas was introduced as initial catalytic performance, followed by sampling every 15 minutes.
3. Catalysts with different metals and different loading amounts are prepared.
Comparative example 1, 0.2wt% Iridium-supported Al 2 O 3 Is a catalyst (201019 b)
An aqueous solution of Ir was prepared in advance with Ir chloride and sodium chloride at a concentration of 0.02g/g, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and the iridium species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface can be prepared into the iridium-loaded Al 2 O 3 Catalyst, labeled Ir (0.2wt％) /Al 2 O 3 。
Comparative example 2, 0.2wt% ruthenium supported Al 2 O 3 Is a catalyst (201019 c)
An aqueous solution of Ru was prepared beforehand with a concentration of 0.02g/g of ruthenium chloride, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out until the solvent is completely evaporated and the ruthenium species is fully supported on Al 2 O 3 The surface can be prepared into the ruthenium-loaded Al 2 O 3 Catalyst, labeled Ru (0.2wt％) /Al 2 O 3 。
Comparative example 3, 0.2wt% rhodium-supported Al 2 O 3 Is a catalyst (201019 d)
An aqueous solution of Rh was prepared in advance as a rhodium nitrate solution at a concentration of 0.02g/g, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and rhodium species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface can be prepared into rhodium-loaded Al 2 O 3 Catalyst, labeled Rh (0.2wt％) /Al 2 O 3 。
Comparative example 4, 0.2wt% platinum-supported Al 2 O 3 Is a catalyst (201022 a)
An aqueous solution of Pt was prepared beforehand at a concentration of 0.02g/g with chloroplatinic acid, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and the platinum species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface can be prepared into the platinum-loaded Al 2 O 3 Catalyst, labeled Pt (0.2wt％) /Al 2 O 3 。
Comparative example 5, 0.2wt% palladium on Al 2 O 3 Is a catalyst (201022 b)
An aqueous solution of Pd was prepared in advance in a concentration of 0.02g/g with a palladium nitrate solution, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out until the solvent is completely evaporated and palladium species are fully loaded on Al 2 O 3 The surface can be prepared into palladium-loaded Al 2 O 3 Catalyst, labeled Pd (0.2wt％) /Al 2 O 3 。
Comparative example 6, 0.5wt% cobalt supported Al 2 O 3 Is a catalyst (200928 g)
Into a round bottom flask was taken 2.47g of cobalt nitrate hexahydrate and dissolved with ethanol, diluted to 84.6g, followed by 99.5g of globular Al 2 O 3 Then spin-evaporating treatment is carried out until the solvent is completely evaporated and cobalt species are fully loaded on Al 2 O 3 The surface can be prepared into cobalt-loaded Al 2 O 3 Catalyst, labeled Co (0.5wt％) /Al 2 O 3 。
Comparative example 7, 0.5wt% iron-supported Al 2 O 3 Catalyst (d 201002 a)
Into a round bottom flask was taken 3.62g of ferric nitrate nonahydrate and dissolved with ethanol, diluted to 84.6g, followed by addition of 99.5g of globular Al 2 O 3 Then spin-steaming treatment is carried out, and when the solvent is completely evaporated and the iron species is fully loaded in Al 2 O 3 The surface can be prepared into the iron-loaded Al 2 O 3 Catalyst, marked Fe (0.5wt％) /Al 2 O 3 。
Comparative example 8, 0.5wt% Nickel-supported Al 2 O 3 Catalyst (d 201002 b)
Into a round bottom flask was taken 2.48g of nickel nitrate hexahydrate and dissolved with ethanol, diluted to 84.6g, followed by 99.5g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and the nickel species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface of the alloy is provided with nickel-loaded Al 2 O 3 Catalyst, labeled Ni (0.5wt％) /Al 2 O 3 。
Comparative example 9, 0.5wt% copper-supported Al 2 O 3 Catalyst (d 201003)
Into a round bottom flask was taken 1.90g of chromium nitrate trihydrate and dissolved in ethanol, diluted to 84.6g, followed by addition of 99.5g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and the copper species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface of the copper-loaded Al alloy is prepared 2 O 3 Catalyst, marked Cu (0.5wt％) /Al 2 O 3 。
Example 1: CN coated 0.2wt% Iridium supported Al 2 O 3 201020 d)
Into a round bottom flask were charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Ir (0.2wt％) /Al 2 O 3 Subsequently, spin-steaming treatment is carried out until the solvent is completely evaporated, so that ZIF-8 is fully coated on Ir (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Ir (0.2wt％) /Al 2 O 3 Marked as CN@Ir (0.2wt％) /Al 2 O 3 。
Example 2: CN coated 0.2wt% ruthenium supported Al 2 O 3 201020 e)
Into a round bottom flask was added a methanol dispersion of ZIF-860g and 15g of small spherical Ru (0.2wt％) /Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on Ru (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the Ru coated by CN (0.2wt％) /Al 2 O 3 Marked as CN@Ru (0.2wt％) /Al 2 O 3 。
EXAMPLE 3 CN coated 0.2wt% rhodium-supported Al 2 O 3 201020 f)
Into a round bottom flask was charged 60g and 15g of spherical Rh as a methanol dispersion of ZIF-8 (0.2wt％) /Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated to fully coat the ZIF-8 on Rh (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Rh (0.2wt％) /Al 2 O 3 Marked as CN@Rh (0.2wt％) /Al 2 O 3 。
EXAMPLE 4 CN coated 0.2wt% platinum-supported Al 2 O 3 Is a catalyst (201023 d)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Pt (0.2wt％) /Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Pt (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the Pt coated by the CN (0.2wt％) /Al 2 O 3 Marked as CN@Pt (0.2wt％) /Al 2 O 3 。
EXAMPLE 5 CN coated 0.2wt% Palladium-supported Al 2 O 3 Is a catalyst (201210 g)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Pd (0.2wt％) /Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Pd (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the Pd coated by the CN (0.2wt％) /Al 2 O 3 Marked as CN@Pd (0.2wt％) /Al 2 O 3 。
EXAMPLE 6 CN coated 0.5wt% cobalt-supported Al 2 O 3 Is a catalyst (201210 d)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, globular Co (0.2wt％) /Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on Co (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the Co coated by CN (0.2wt％) /Al 2 O 3 Marked as CN@Co (0.2wt％) /Al 2 O 3 。
EXAMPLE 7 CN coated 0.5wt% iron-supported Al 2 O 3 Is a catalyst (201210 e)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Fe (0.2wt％) /Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that ZIF-8 is fully coated on Fe (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the Fe coated with CN (0.2wt％) /Al 2 O 3 Marked as CN@Fe (0.2wt％) /Al 2 O 3 。
EXAMPLE 8 CN coated 0.5wt% Nickel-supported Al 2 O 3 Is a catalyst (201210 f)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Ni (0.2wt％) /Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that ZIF-8 is fully coated on Ni (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the Ni coated by CN (0.2wt％) /Al 2 O 3 Marked as CN@Ni (0.2wt％) /Al 2 O 3 。
EXAMPLE 9 CN coated 0.5wt% copper loaded Al 2 O 3 Is a catalyst (201211 e)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Cu (0.2wt％) /Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Cu (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain CN coated Cu (0.2wt％) /Al 2 O 3 Marked as CN@Cu (0.2wt％) /Al 2 O 3 。
PREPARATION EXAMPLE 1 CN coated Al 2 O 3 Catalyst (201124 k)
Into a round bottom flask were charged 5g of a methanol dispersion of ZIF-8, 5g of methanol and 10g of globular Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (0.5)。
Preparation example 2, CN coated Al 2 O 3 Catalyst (201120 c)
Into a round bottom flask were charged 15g of a methanol dispersion of ZIF-8 and 15g of globular Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (1)。
PREPARATION EXAMPLE 3 CN coated Al 2 O 3 Catalyst (201120 b)
Into a round bottom flask was charged 30g of a methanol dispersion of ZIF-8 and 15g of globular Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that ZIF-8 is fully coatedAl 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (2)。
PREPARATION EXAMPLE 4 CN coated Al 2 O 3 Catalyst (201015 e)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, globular Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (4)。
PREPARATION EXAMPLE 5 CN coated Al 2 O 3 Catalyst (201124 l)
Into a round bottom flask was charged 200g of a methanol dispersion of ZIF-8 and 10g of globular Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (20)。
Preparation example 6, CN coated Al 2 O 3 Catalyst (201211 a)
Into a round bottom flask were charged 60g and 15g of a methanol dispersion of ZIF-8 as pentadentate spherical Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 。
PREPARATION EXAMPLE 7 CN coated NaY catalyst (201211 c)
Adding 60g and 15g of small spherical NaY molecular sieve of ZIF-8 methanol dispersion into a round bottom flask, and then performing rotary evaporation treatment until the solvent is completely evaporated to ensure that the ZIF-8 is fully coated on the NaY surface, and then performing N at 600 DEG C 2 And pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated NaY, wherein the CN coated NaY is marked as CN@NaY.
Preparation example 8 CN coated TiO 2 Catalyst (201211 d)
Into a round bottom flask was charged 60g and 15g of short bar-shaped TiO as a methanol dispersion of ZIF-8 2 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the TiO 2 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the TiO coated by CN 2 Marked as CN@TiO 2 。
Application test embodiment and results
1. The activity test was performed in the manner of the preparation example, differing from the test of CN109225306a in that pure propane alkane gas was used, and CN109225306a was 5% propane gas (see patent example 24, tables 5 and 0065). The test results were as follows:
table 1 propane dehydrogenation application test experimental and comparative data
From table 1, it can be concluded that the catalyst of the present invention significantly improves the catalytic activity, and that even the catalyst containing Fe, pt and Pd, which has poor catalytic activity, has significantly improved conversion and selectivity, compared to the catalyst not coated with CN.
2. Product structure characterization
The prepared examples, intermediates and raw material products are characterized, the photographs of fig. 1-4 are prepared, and the photographs can show that the surface color of the catalyst is changed and the coating effect is displayed after ZIF coatings with different coating amounts and pyrolysis.
FIG. 1 shows the change in appearance of the alumina pellets, coated with ZIF-8 (at different levels), pyrolyzed to CN coated alumina pellets, where B1-B5 show the appearance of alumina pellets of different coating concentrations (essentially white) and C1-C5 show the appearance of alumina pyrolyzed to CN coated (C1 yellow, C2 brown, C3 dark brown, C4 black, C5 black, respectively).
FIG. 2 is an appearance of different carriers and different shaped carriers at different stages, including carriers (A1-A4) -ZIF-8 coated (B1-B4) -pyrolysis to form CN coated carriers (C1-C4). Wherein (A1) is a small spherical Al 2 O 3 White, (A2) five-tooth spherical Al 2 O 3 White, (A3) small sphere NaY molecular sieve light yellow, (A4) short rod-shaped TiO 2 White; coated (B1) globular ZIF-8@Al 2 O 3 White, (B2) five-tooth spherical ZIF-8@Al 2 O 3 White, (B3) small sphere ZIF-8@NaY molecular sieve light yellow, (B4) short rod-shaped ZIF-8@TiO 2 Pale yellow; pellets CN@Al after pyrolysis (C1) 2 O 3 Black, (C2) pentadentate sphere cn@al 2 O 3 Grey, (C3) globular CN@NaY molecular sieve black, (C4) CN@ short bar-shaped TiO 2 Grey.
FIG. 3 is a graph showing the change in appearance of catalysts before and after loading with different active metals, respectively (A) Al 2 O 3 White; after loading metal, (B1) Ir/Al is obtained 2 O 3 Pale yellow, (B2) Rh/Al 2 O 3 Yellow, (B3) Ru/Al 2 O 3 Light brown, (B4) Co/Al 2 O 3 Light pink; after coating, (C1) ZIF-8@Ir/Al is obtained 2 O 3 Pale yellow, (C2) ZIF-8@Rh/Al 2 O 3 Pale yellow; (C3) ZIF-8@Ru/Al 2 O 3 Off-white, (C4) ZIF-8@Co/Al 2 O 3 Purple powder; after pyrolysis, black (D1) CN@Ir/Al is obtained 2 O 3 ，(D2)CN@Rh/Al 2 O 3 ，(D3)CN@Ru/Al 2 O 3 ，(D4)CN@Co/Al 2 O 3 。
FIG. 4 shows the microstructure of the feedstock and product at different stages dynamically, A-C shows the surface morphology of alumina, D-F shows the surface visible as ZIF-8 after coating with ZIF-8, and G-I shows the microstructure of the catalyst surface after pyrolysis.
The foregoing examples of the present invention are provided for the purpose of clearly illustrating the present invention and are not to be construed as limiting the embodiments of the present invention, and other and different forms of variation or modification may be made by those skilled in the art based on the foregoing description, and it is not intended to be exhaustive of all the embodiments, and all obvious variations or modifications which come within the scope of the invention are defined by the appended claims.
Claims (15)
1. Have CN@M 1 A catalyst of Zn/carrier structure, wherein M metal is selected from one or more of noble metal atoms selected from Pt, au, ru, rh, pd, ir or Ag or transition metals selected from Fe, co, mn, ni or Cu, M 1 Indicating that the metal exists in a single atom site state, the M content in the catalyst is 0.01-10wt% based on the weight of the catalyst,
zn content is 0.01-20wt% based on the weight of the catalyst;
the carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silica-alumina, titanium oxide or a mixture of any two or more of the above; the carrier is shaped into a molded structure, and the molded structure comprises a sphere, a strip, a cylinder, a multi-hollow channel and a honeycomb body;
CN@ the carbon nitrogen layer wrap;
the catalyst is prepared by the following method, which comprises the following steps:
step one: m metal active components are loaded on a carrier to form a catalyst precursor;
step two: coating the catalyst precursor with ZIF-8;
step three: in vacuum, inert gas or H 2 Pyrolyzing in atmosphere at 400-800 ℃;
the M metal active component is loaded on the carrier in a metal precursor mode, and the M metal precursor is inorganic metal salt, organic metal salt or complex.
2. The catalyst of claim 1, wherein the M metal content in the catalyst is 0.05-5wt% based on the weight of the catalyst; zn content is 0.05-10wt% based on the weight of the catalyst.
3. The catalyst of claim 1 wherein the M metal content in the catalyst is from 0.1 to 1wt% based on the weight of the catalyst; zn content is 0.1-5wt% based on the weight of the catalyst.
4. A catalyst as claimed in any one of claims 1 to 3 wherein the M metal is Pt, ru, pd, ir or Rh.
5. The catalyst of claim 4 wherein the support is an alumina, molecular sieve or titania support.
6. A method of preparing the catalyst of any one of claims 1-5, comprising:
step one: m metal active components are loaded on a carrier to form a catalyst precursor;
step two: coating the catalyst precursor with ZIF-8;
step three: in vacuum, inert gas or H 2 Pyrolysis is carried out in the atmosphere, and the pyrolysis temperature is 400-800 ℃.
7. The method of claim 6, wherein in step one, the M metal active component is supported on a carrier in the form of a metal precursor, and the M metal precursor is an inorganic metal salt, an organic metal salt or a complex.
8. The method of claim 6, wherein in the second step, the ZIF-8 is coated on the surface of the precursor by using a dipping and spin-steaming mode.
9. The process of claim 6, wherein in step three, the pyrolysis temperature is 450-800 ℃.
10. The method of claim 7, wherein the M metal precursor is a nitrate, chloride, sulfate, acetate, oxalate, acetylacetonate, or chloride complex of M metal.
11. Have CN@M 1- A method for regenerating a Zn/support structured monoatomic catalyst, the method comprising:
step A: removal results in a device having a cn@m as claimed in claim 1 1- A Zn/support structure catalyst poisoned or deactivated species forming a catalyst containing precursor;
and (B) step (B): coating a catalyst precursor to be regenerated by ZIF-8, and coating by a dipping or rotary steaming mode;
step C: in vacuum, inert gas or H 2 Pyrolyzing in atmosphere at 400-800 ℃;
wherein step A removes the inactivating substance by a conventional method comprising using O 2 Removal by air oxidation, or by use of H 2 、CO 2 Removing water vapor and inactivating substances through reaction;
m metal is selected from one or more of noble metal atoms or transition metals, wherein the noble metal atoms are selected from Pt, au, ru, rh, pd, ir or Ag and the transition metals are selected from Fe, co, mn, ni or Cu; the carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silica-alumina, titanium oxide or a mixture of any two or more of the above;
the M metal active component is loaded on a carrier in the form of a metal precursor, and the M metal precursor is nitrate, chloride, sulfate, acetate, oxalate, acetylacetonate or chlorine complex of M metal.
12. The regeneration method of claim 11, wherein step a uses air oxidation to remove the deactivating species.
13. The regeneration method according to claim 11, wherein the carrier is alumina, molecular sieve, titanium oxide carrier.
14. Use of the catalyst of any one of claims 1-5 or the catalyst prepared by the method of any one of claims 6-10 for catalyzing the dehydrogenation of an alkane to form an alkene, the alkane being C 2-6 Alkane, dehydrogenation to obtain C 2-6 An olefin.
15. A process for the preparation of olefins by dehydrogenation of alkanes comprising preparing cn@m using the catalyst of any of claims 1-5 or the process of any of claims 6-10 1- Zn/carrier structure catalyst for catalyzing alkane dehydrogenation to form alkene, wherein the alkane is C 2-6 Alkanes, the olefins being C 2-6 An olefin.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126774A (en) * | 2017-06-15 | 2019-01-04 | 中国科学院大连化学物理研究所 | A kind of monatomic noble metal catalyst of super high-dispersion loading type and preparation method thereof |
| CN109225306A (en) * | 2018-10-26 | 2019-01-18 | 清华大学 | Monatomic catalyst and catalysis process for low-carbon dehydrogenation of hydrocarbons producing light olefins |
| CN110339851A (en) * | 2019-07-15 | 2019-10-18 | 浙江师范大学 | The catalyst and preparation method thereof of preparation 2,3,5-trimethylhydroquinone is hydrogenated for 2,3,5-trimethylbenzoquinoe |
| CN110449177A (en) * | 2019-08-19 | 2019-11-15 | 中国科学技术大学 | A kind of multifunctional single catalyst atom and preparation method thereof for air comprehensive purification |
| CN110479349A (en) * | 2019-09-10 | 2019-11-22 | 辽宁星空新能源发展有限公司 | A method of preparing the all-hydrolytic catalyst in the monatomic double activated site of palladium |
| CN111420691A (en) * | 2020-03-20 | 2020-07-17 | 南方科技大学 | Metal monoatomic catalyst and preparation method thereof |
| CN112138720A (en) * | 2020-09-15 | 2020-12-29 | 中国科学院青岛生物能源与过程研究所 | Amino-modified transition metal monoatomic catalyst system, preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150209759A1 (en) * | 2012-07-26 | 2015-07-30 | Saudi Basic Industries Corporation | Alkane dehydrogenation catalyst and process for its preparation |
| CN107008479B (en) * | 2016-06-23 | 2019-10-18 | 北京大学 | Metal/α-MoC1-xSupport type single atomic dispersion catalyst, its synthetic method and application |
-
2020
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126774A (en) * | 2017-06-15 | 2019-01-04 | 中国科学院大连化学物理研究所 | A kind of monatomic noble metal catalyst of super high-dispersion loading type and preparation method thereof |
| CN109225306A (en) * | 2018-10-26 | 2019-01-18 | 清华大学 | Monatomic catalyst and catalysis process for low-carbon dehydrogenation of hydrocarbons producing light olefins |
| CN110339851A (en) * | 2019-07-15 | 2019-10-18 | 浙江师范大学 | The catalyst and preparation method thereof of preparation 2,3,5-trimethylhydroquinone is hydrogenated for 2,3,5-trimethylbenzoquinoe |
| CN110449177A (en) * | 2019-08-19 | 2019-11-15 | 中国科学技术大学 | A kind of multifunctional single catalyst atom and preparation method thereof for air comprehensive purification |
| CN110479349A (en) * | 2019-09-10 | 2019-11-22 | 辽宁星空新能源发展有限公司 | A method of preparing the all-hydrolytic catalyst in the monatomic double activated site of palladium |
| CN111420691A (en) * | 2020-03-20 | 2020-07-17 | 南方科技大学 | Metal monoatomic catalyst and preparation method thereof |
| CN112138720A (en) * | 2020-09-15 | 2020-12-29 | 中国科学院青岛生物能源与过程研究所 | Amino-modified transition metal monoatomic catalyst system, preparation method and application thereof |
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