CN106693986A - High specific surface area enhanced integrated alumina supported iron-manganese binary catalyst - Google Patents
High specific surface area enhanced integrated alumina supported iron-manganese binary catalyst Download PDFInfo
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- CN106693986A CN106693986A CN201710041975.2A CN201710041975A CN106693986A CN 106693986 A CN106693986 A CN 106693986A CN 201710041975 A CN201710041975 A CN 201710041975A CN 106693986 A CN106693986 A CN 106693986A
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- Prior art keywords
- mould
- catalyst
- precursor
- manganese
- temperature
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 92
- 239000000463 material Substances 0.000 claims abstract description 56
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 46
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011572 manganese Substances 0.000 claims abstract description 43
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 239000012692 Fe precursor Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000011049 filling Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims description 33
- 238000002788 crimping Methods 0.000 claims description 30
- 230000003319 supportive effect Effects 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000004411 aluminium Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000012512 characterization method Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 229920002907 Guar gum Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
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- 235000010417 guar gum Nutrition 0.000 claims description 4
- 229960002154 guar gum Drugs 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
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- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
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- 238000001291 vacuum drying Methods 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004277 Ferrous carbonate Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 229920000926 Galactomannan Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- GDNPTWMUGVAHOS-UHFFFAOYSA-N [Fe].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN GDNPTWMUGVAHOS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
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- FUSJZTVOKYJFPI-UHFFFAOYSA-N cyclopentane;iron;5-methylcyclopenta-1,3-diene Chemical compound [Fe].[CH-]1[CH-][CH-][CH-][CH-]1.C[C-]1C=CC=C1 FUSJZTVOKYJFPI-UHFFFAOYSA-N 0.000 claims description 2
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- -1 ferrimanganic binary Chemical compound 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 2
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- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
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- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018575 Al—Ti Inorganic materials 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysis and relates to a high specific surface area enhanced integrated alumina supported iron-manganese binary catalyst, comprising a catalyst preparation method and catalyst product characteristics. The following raw materials are used in the catalyst preparation method: an aluminum precursor, an iron precursor, a manganese precursor, a first additive, a second additive, an acid solution and a supporting material; and an integrated catalyst forming die is used. The method comprises the following steps: 1, preparing formed precursors; 2, filling inclusion; 3, applying pressure to the inclusion; and 4, performing programmed calcinations on formed blocks. The catalyst product obtained by the preparation method has the following characteristics that a single catalyst is large in bulk mass; the overall specific surface area of the catalyst is large; the total mass content of the elements iron and manganese in the catalyst can reach 0.6-20%; and an X-ray diffraction peak of the catalyst only comprises the spectral characteristics of alumina and does not comprise spectral characteristics related to the iron or manganese component. The catalyst product is high in mechanical strength.
Description
Technical field
The invention belongs to catalysis technical field, it is related to a kind of integral alumina load ferrimanganic binary catalyst, specifically,
It is the increasing with high-specific surface area by ferrimanganic binary precursor, supportive material and alumina precursor moulded pottery not yet put in a kiln to bake one-shot forming to be related to a kind of
Strong type integral alumina load ferrimanganic binary catalyst product and preparation method thereof.
Background technology
Catalyst is the core science and technology problem of catalytic process.The solid catalyst commonly used in industry can be divided into particle
Or powder catalyst, integral catalyzer and the catalyst with given shape, among these with particle or powdered catalytic
Agent is most commonly seen.Loaded catalyst is especially common in particle or powdered, and this is because the carrier of loaded catalyst is mostly
Some porous materials, such as aluminum oxide, silica gel, activated carbon, molecular sieve, exist with powder or graininess more.But it is overall
Formula catalyst has some advantages of itself for powder or pellet type catalyst, but after its application surface is not so good as at present
Person is extensive.Its main cause is that integral catalyzer developing history is relatively short, and preparation technology is relatively complicated, technology path
Seldom.Iron（Fe）Base catalyst and manganese（Mn）Base catalyst is all common catalyst type in industrial production.Two kinds of catalysis are lived
Property component be used in combination to form two-element active component, however, it would be possible to the different catalysis of different metal component are comprehensively risen
Come, double-function catalyzing effect may be played.Iron-manganese composite catalyst can be used to be catalyzed the advanced oxidation of organic pollution.It is former
In reason, the manganese component of high-valence state can be by oxidation operation, while itself being reduced into lower valency manganese component；And iron component is for normal
With oxidants hydrogen peroxide have catalytic decomposition activity, its using be conducive to produce free oxygen atom；Free oxygen atom can be with
Lower valency manganese component is oxidized to high oxidation state manganese component, while completing a catalytic cycle.Therefore comprehensively apparently, monoblock type is developed
The preparation method of support type ferrimanganic binary catalyst has important potential using value with Related product.
Patent CN102407130A discloses the composite oxide supported entirety on ceramic honeycomb of a kind of Co, Mn, Ce
Formula catalyst.The invention first prepares CeO2Coating, and two kinds of components of Co, Mn are attached to by CeO by infusion process2In coating；Then
By Co, Mn, CeO2Coating is coated on ceramic honeycomb.Specific letter of the invention without correlation integral catalyzer specific surface area
Breath, but it may be speculated that because the specific surface area of the ceramic honeycomb commonly used is relatively low, therefore whole specific surface area of catalyst will be received
To larger limitation.Organic the reported document in Chinese Academy of Sciences Chengdu【Zhang Zhiqiang etc., for the CuMnCeZr/ of benzene catalysis burning
The preparation of Al-Ti integral catalyzers and sign, petrochemical industry, volume 2010,39,10 phases, 1157-1161 pages】There is provided one kind
Alumina load type multi-element metal component integral catalyzer preparation method containing Mn.The technology path of the preparation method is first logical
Cross infusion process and prepare the component catalyst powder of alumina load Cu, Mn, Ce, Zr tetra-, then disperse to be made with water by ball milling
Slurry, and slurry is coated on cordierite carrier.Similar foregoing invention patent, this report is without correlation integral catalyzer specific surface area
Specifying information.It may be speculated that because cordierite specific surface area is relatively low from principle, therefore whole specific surface area of catalyst also will
By larger limitation.
For the preparation technology of integral supported type catalyst, also there is this improvement preparation method in this area
Technical need, especially to preparing high-specific surface area, good mechanical strength, high metal component decentralization, multiple active components, low
The demand of running cost process.
The content of the invention
The present invention proposes a kind of high-specific surface area enhanced integral alumina load ferrimanganic binary catalyst and its system
Preparation Method, its technology path is the mixing moulded pottery not yet put in a kiln to bake for first making salic precursor, iron precursor and manganese precursor, then by adding branch
Support property material obtains the inclusion enclave of precursor and supportive material, then by mould compression forming, then by fine program
Roasting obtains the technology path of product.By the technology path can obtain high-specific surface area, it is microcosmic on possess nanoscale duct,
The integral alumina load ferrimanganic binary catalyst of high mechanical properties；The preparation method is come without expensive device, raw material simultaneously
Source is simple, more friendly environment, safe operation, cost are relatively low.Realizing the concrete technical scheme of above-mentioned technology path is：
A kind of enhanced integral alumina load ferrimanganic binary catalyst of high-specific surface area, comprising method for preparing catalyst with urge
Agent product feature；Wherein method for preparing catalyst uses the following raw material：
Aluminum precursor：One kind of aluminium hydroxide, boehmite, or above-mentioned substance arbitrary proportion mixture；
Iron precursor：Be frerrous chloride, iron chloride, ferrous nitrate, ferric nitrate, ferrous sulfate, ferric sulfate, ferrous acetate, ferric acetate,
Ferrous carbonate, ferric carbonate, iron hydroxide, ferrous oxalate, ferric oxalate, ferric acetyl acetonade, ferrocene, methyl ferrocene, ethyl two
One kind in luxuriant iron, ethylenediamine tetra-acetic acid-iron complex, or above-mentioned substance arbitrary proportion mixture；
Manganese precursor：It is manganese sulfate, manganese chloride, manganese nitrate, manganese carbonate, manganese acetylacetonate, sodium ethylene diamine tetracetate manganese, ethylenediamine tetraacetic
One kind in manganese acetate, manganese oxalate, or the mixture that above-mentioned substance is mixed with arbitrary proportion；
First additive：It is sesbania powder, sesbania gum, guar gum, cation guar gum, sodium alginate, carboxymethylcellulose calcium, carboxylic second
One kind in base cellulose, sodium carboxymethylcellulose, sodium hydroxyethlcellulose, galactomannans, or above-mentioned substance is any
The mixture of ratio；
Second additive：Be ethanol, propyl alcohol, butanol, ethylene glycol, propane diols, polyethylene glycol, polyvinyl alcohol, glucose, fructose,
Sucrose, maltose, cellobiose, granularity are less than the carbon black of 60 mesh, granularity less than the one kind in the water soluble starch of 60 mesh,
Or the mixture of above-mentioned substance arbitrary proportion；
Acid solution：A kind of aqueous solution, contains nitric acid, sulfuric acid, hydrochloric acid, acetic acid, oxalic acid, phosphoric acid, citric acid, maleic acid, tartaric acid
In one or more materials, the pH value of the aqueous solution is in the range of 0.0 ~ 4.0；
Supportive material：One kind in wire, bonding jumper, sheet metal, wire netting or carbon fiber, or the above-mentioned type material
It is applied in combination with arbitrary proportion；The material of wherein metal be ferrimanganic binary, stainless steel, ferrimanganic binary, chromium, ferrimanganic binary, zinc,
A kind of or based on above-mentioned material alloy material in aluminium, titanium, manganese；Metal material species can be one kind of above-mentioned material,
Or various be applied in combination with arbitrary proportion；For wire, bonding jumper or carbon fiber, its stretched length is not less than 1 cm；
For sheet metal or wire netting, its circumference projected area is not less than 0.1 cm2。
Above-mentioned method for preparing catalyst, uses integral catalyzer mould；The mould includes mould the 1st
Part, the part of mould second and the part of mould the 3rd；The part of mould first includes a cylindrical cavity；The part of mould second is included
Mould the second part crimping section and mould the second part pressure-bearing part；The geometry of mould the second part crimping section is circle
Cylinder, it has a compressive plane, and the geometry of the compressive plane is circle；Mould the second part pressure-bearing part has one and holds
Pressure surface；The part of mould the 3rd includes the part crimping section of mould the 3rd and the part pressure-bearing part of mould the 3rd；The part of mould the 3rd
The geometry of crimping section is cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；Mould the 3rd
Part pressure-bearing part has a pressure-bearing surface；The compressive plane of mould the second part crimping section and the part crimping section of mould the 3rd
The axis direction of cylindrical cavity that can be included from the part of mould first of compressive plane be put into.
Above-mentioned method for preparing catalyst, by above-mentioned raw materials and integral catalyzer mould, its preparation method bag
Containing following steps：
Step one, prepare molding precursor；
Step 2, filling inclusion enclave；
Step 3, to inclusion enclave apply pressure；
Step 4, the roasting of the program of formed blocks.
The specific method of aforementioned four step is as follows：
Step one, prepare molding precursor；Specific method is as follows：
Take aluminum precursor, iron precursor, manganese precursor, the first additive, second additive of certain mass；Iron content unit wherein in iron precursor
The ratio between molal quantity containing aluminium element is 0.003 ~ 0.12 in the molal quantity and aluminum precursor of element；In manganese precursor containing manganese element mole
The ratio between molal quantity containing aluminium element is 0.003 ~ 0.12 in number and aluminum precursor；Iron precursor and ferro element and manganese element in manganese precursor
Total mole number and aluminum precursor in the ratio between molal quantity containing aluminium element be less than 0.18；The quality of the first additive is aluminum precursor matter
0.01 ~ 0.1 times of amount；The quality of the second additive is 0 ~ 0.2 times of aluminum precursor quality；Five kinds of materials uniformly mix, and obtain
To mixed-powder；Acid solution is then poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is aluminium
0.5 ~ 1.3 times of precursor mass；Kneading is carried out to dough by hand or banded extruder so that aluminum precursor therein,
First additive, the second additive, acid solution further uniformly mix, and form a moulded pottery not yet put in a kiln to bake, do not have obvious drop on moulded pottery not yet put in a kiln to bake；
The moulded pottery not yet put in a kiln to bake referred to as molding precursor obtained by said mixture kneading.
Step 2, filling inclusion enclave；Specific method is as follows：
Molding precursor described in the step of taking certain mass one, its quality is in the range of 2 ~ 400g；Take the supportive of certain mass
Material, its quality is 0.01 ~ 0.6 times of molding precursor quality；Molding precursor is filled into entirety together with supportive material
In the cylindrical cavity that formula shaping of catalyst the first part of mould is included；Filling rear support material is formed precursor parcel；
Inclusion enclave is formed after molding precursor parcel supportive material；By mould the second part crimping section and the part press section of mould the 3rd
The both sides of the cylindrical cavity for being included from the part of mould first respectively are divided to load；Load inclusion enclave material requested and place mould
The order of the second part or the part of mould the 3rd is not limited；Compressive plane, the part of mould the 3rd when mould the second part crimping section
The compressive plane of crimping section is collectively forming an airtight cavity with the cylindrical empty cavity wall that the part of mould first is included, and will
Above-mentioned inclusion enclave is enclosed in the airtight cavity, completes to load step.
Step 3, to molding precursor apply pressure；Specific method is as follows：
The integral catalyzer mould combination that inclusion enclave will be assembled is placed on a hydraulic press, mould the second part pressure-bearing
Partial pressure-bearing surface, the pressure-bearing surface of the part pressure-bearing part of mould the 3rd are contacted with the applying press member of hydraulic press so that hydraulic pressure
Machine pressure applied can act on above-mentioned two pressure-bearing surface；The pressure size of applying is in the range of 0.1 ~ 5 MPa；Apply
Pressure time is in the range of 20 s ~ 4 h；The molding precursor after being pressurized then is taken out from mould and obtains formed blocks.
Step 4, the roasting of the program of formed blocks；Specific method is as follows：
Operation is dried to formed blocks described in step 3, part volatility moisture is left formed blocks with other materials,
Until the dried quality of formed blocks is less than 85% before drying；Drying process including but not limited to drying, dry in atmosphere
Drying in case or Muffle furnace, dry in vacuum drying chamber, dry in drier, blowing drying, daylight is dried, infrared lamp is dried,
The operations such as centrifuge drying, or any combination of aforesaid operations is operated；Formed blocks are placed in into one afterwards has temperature programmed control
It is calcined in the heater of function；The atmosphere of roasting is air, or purity oxygen, or any oxygenous ratio is mixed more than 20%
Close gas；Temperature and time relation in program roasting includes three temperature controlling stages, is referred to as the first temperature control stage, the
Two temperature control stages and the 3rd temperature control stage；First temperature control stage had an initial temperature, and its value is 20 ~ 150oIn the range of C
Certain value, with a final temperature, its value is 300 ~ 750oCertain value in the range of C；First temperature control stage is from starting
Temperature is to final temperature average ramp rate 0.5 ~ 8oIn the range of C/min；The total time of the first temperature controlling stages exists
In the range of 30 min ~ 12 h；Second temperature control stage had an initial temperature, and its value is 300 ~ 750oCertain in the range of C
Individual value, with a final temperature, its value is also 300 ~ 750oCertain value in the range of C；Second temperature control stage is warm from starting
Final temperature average ramp rate is spent -2 ~ 2oIn the range of C/min；The total time in the second temperature control stage is in 1 ~ 6 h
In the range of；3rd temperature control stage had an initial temperature, and its value is 300 ~ 750oCertain value in the range of C, with one
Final temperature, its value is 20 ~ 150oCertain value in the range of C；3rd temperature control stage is average from initial temperature to final temperature
Rate of temperature change is -8 ~ -0.5oIn the range of C/min；The total time in the 3rd temperature control stage is in the range of 2 ~ 24 h.
Complete after step 4, formed blocks are converted into the enhanced integral alumina of final products, i.e. high-specific surface area
Load ferrimanganic binary catalyst；Preparation process is completed.
By the sign to above-mentioned final products, the enhanced monoblock type of the product of above-mentioned preparation method, i.e. high-specific surface area
Alumina load ferrimanganic binary catalyst, is also provided simultaneously with following product feature：
（1）The quality of single catalyst block is up to 1 ~ 100 g；
（2）The overall specific surface area of catalyst is 150 ~ 550 m2/g；
（3）Iron, the manganese element gross mass content of catalyst are up to 0.6 ~ 20 %；
（4）The X-ray diffraction peak of catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of and iron component or manganese component phase
The SPECTROSCOPIC CHARACTERIZATION of pass.
Above-mentioned（2）（3）（4）Point feature, the result contribution not comprising supportive material；This is due to these characterization results
For the local sampling of catalyst sample is characterized, supportive material is avoided during sign.
Because the X-ray diffraction peak SPECTROSCOPIC CHARACTERIZATION of aluminum oxide is known to those skilled in the art, therefore the present invention need not be given.
It is above-mentioned（3）、（4）2 points of comprehensive explanations, while with considerable ferrimanganic binary composition load capacity, the tuple of ferrimanganic two
Point there is decentralization very high on microcosmic.It is noted that the characterization test method of the present invention and non-protected product, but protection
The due feature of product obtained by the present invention.What the characterization test method used by this product was all commonly used for those skilled in the art
Method.
In above-mentioned relevant second additive, the representation of " 60 mesh " that moieties contain, used this area for
A kind of idiomatic expression method of grain or powdered solid substance particle size.In the art, " mesh number " represents a tool
There is the grid number contained by the screen cloth per inch for being uniformly distributed co-ordination.Certain particle can illustrate this by such screen cloth
Particle size is less than the size of the defined of related mesh number.For example, a screen cloth for 60 mesh, if having being uniformly distributed co-ordination,
The grid number that each inch contains is 60；If certain particle can be can be expressed as the particle size and be less than by such screen cloth
60 mesh, specifically, size is less than 1 inch/60=2.54 cm/60=0.0423 cm.
Hydraulic press is the usual means in industry and laboratory research, refers to one kind with liquid as working media, is used for
Energy or pressure is transmitted to realize polytechnic machine.The present invention realizes applying one to being extruded object both sides using hydraulic press
Fixed pressure, the particular type specification for hydraulic press does not do any limitation.
" operation is dried to formed blocks described in step 3 " in for above-mentioned steps four, it should be noted that in ability
In domain or even in various fields, it is a kind of common routine that the solid matter of moisture content or other volatile materials is dried
Operation.The basic object of drying process is part or all of moisture or other volatile materials is left solid.Usual solids
Matter is dried, and in addition to being placed in and being dried naturally in air, can also be dried up using hair-dryer, oven for drying, and infrared lamp dries
Dry, the sun is dried, vacuum drying chamber drying, is placed in drier and the operating method such as is dried, or aforesaid operations is any
Combination operation.Therefore, if be dried to formed blocks using above-mentioned any one operation or various operative combinations so that
The dried mass ratio of formed blocks is reduced to 85% or less before drying, and equivalence operation is belonged in the present invention.
" having the heater of temperature programmed control function " described in above-mentioned steps four is catalyst, solid material preparation field
In commonly use a kind of equipment, i.e., the Temperature-time relation that its temperature that can be realized in a heater is previously set according to certain
Curvilinear motion；The concrete form freedom of heater, can be but not limited to tube furnace, Muffle furnace, baking oven, electric furnace etc..
Average ramp rate is defined as follows in above-mentioned steps four：If in certain moment t1When thermometric object temperature value
It is T1, in another moment t2When thermometric object temperature value be T2, wherein t2In t1Afterwards, then from t1To t2This period
Interior, average ramp rate can be expressed as the business of temperature change value and time change value, i.e. (T2-T1)/(t2-t1).If warm
Degree is with Celsius' thermometric scaleoC or thermodynamic scale K is unit, and the time, the unit of average ramp rate was in units of minoC/
Min or K/min.HereoC/min is identical with the value of K/min.It is clear that also having other normal due to temperature and time
With unit, those skilled in the art can voluntarily carry out the conversion of unit.
" specific surface area " of material is the basic conception in Surface Science, is also the conventional physical quantity in this area, is referred to
It is the size of surface area that the material of unit mass has.This area measure side conventional for material " specific surface area "
Method is based on low temperature nitrogen adsorption-desorption isothermal, then by Brunauer-Emmett-Teller method substance for calculations
Specific surface area（Result is frequently referred to BET specific surface area）；Such Adsorption and desorption isotherms can also obtain the hole contained by solid matter
The information such as size and distribution situation, especially nanoscale Jie view hole road size and the information of distribution.
The positive effect of the present invention is as follows：
（1）Enhanced integral alumina loads the preparation process is simple of ferrimanganic binary catalyst, and raw material are cheap, running cost
It is low, it is suitable for large-scale production；Compared with the existing monoblock type ground of most of utilizations then coats catalytic component, one-shot forming
Reduce processing step number；Enhanced integral alumina load ferrimanganic binary catalyst and ordinary unit alumina load
Type catalyst is compared, and its mechanical strength is greatly improved so that later stage service life is longer.
（2）Preparation technology is environment-friendly, and in addition to using a certain amount of inorganic acid or organic acid, other materials is substantially all
It is nontoxic, non-corrosiveness material；And the inorganic acid and organic acid listed by technical scheme are all more conventional chemical substances, it makes
It is that those skilled in the art know with method, points for attention.
（3）Existing most of integral catalyzer specific surface areas are relatively low（Often it is less than<20 m2/g）, and enhancing of the invention
The specific surface area of type integral alumina load ferrimanganic binary catalyst may be up to 550 m2/g.By supportive material institute accounting
Example is smaller, influences smaller to total body surface area.Product also has substantial amounts of nanoscale Jie view hole road, makes it have good urging
Change, adsorption applications prospect.
Brief description of the drawings
The integral catalyzer mould schematic diagram of accompanying drawing 1.；1 is the part of mould first；2 is the part of mould second；3 are
The part of mould the 3rd；4 is the cylindrical cavity that the part of mould first is included；5 be the part of mould first institute comprising cylindrical empty
The geometrical axis in chamber 4, the axis only to facilitate understand and draw, and non-actual existence；6 is mould the second part press section
Point；7 is mould the second part pressure-bearing part；8 is the compressive plane of mould the second part crimping section；9 is that the part of mould second holds
The pressure-bearing surface of laminate section；10 is the part crimping section of mould the 3rd；11 is the part pressure-bearing part of mould the 3rd；12 is mould the 3rd
The compressive plane of part crimping section；13 is the pressure-bearing surface of the part pressure-bearing part of mould the 3rd；14 representatives are enclosed within the first part institute
Comprising cylindrical cavity 4 inside molding precursor；8th, 9,12,13 4 directions of arrow are also represented when mould is integrally subject to outer
After power extruding, the Impact direction of mould is illustrated.
Specific embodiment
Embodiment one,
A kind of enhanced integral alumina load ferrimanganic binary catalyst of high-specific surface area, comprising method for preparing catalyst with urge
Agent product feature；Wherein preparation method uses the following raw material：
Aluminum precursor：Aluminium hydroxide；
Iron precursor：Iron chloride；
Manganese precursor：Manganese sulfate；
First additive：The mixture of sesbania powder and sodium hydroxyethlcellulose, the two mass ratio is 4.5 to 1；
Second additive：Carbon black of the granularity less than 60 mesh；
Acid solution：PH value is 0.5 nitric acid and oxalic acid mixed aqueous solution, and wherein the ratio between nitric acid and oxalic acid material mole is 1 ratio
1；
Supportive material：Stainless steel strip, length is for about 2.5 cm；The cm of its sectional area about 0.032。
Method for preparing catalyst described in the present embodiment, uses integral catalyzer mould；The mould works
When as shown in Figure 1；The mould includes the first part of mould 1, the second part of mould 2 and the part 3 of mould the 3rd；Mould
One part includes a cylindrical cavity 4；The second part of mould 2 includes the second part of mould crimping section 6 and mould the 2nd 0
Part pressure-bearing part 7；The geometry of the second part of mould crimping section 6 is cylinder, and it has a compressive plane 8, the extruding
The geometry in face 8 is circle；Mould the second part pressure-bearing part 7 has a pressure-bearing surface 9；The part 3 of mould the 3rd includes mould
Have the 3rd part crimping section 10 and the part pressure-bearing part 11 of mould the 3rd；The geometry of the part crimping section 10 of mould the 3rd
It is cylinder, it has a compressive plane 12, and the geometry of the compressive plane 12 is circle；The part pressure-bearing part 11 of mould the 3rd
With a pressure-bearing surface 13；The compressive plane 8 of mould the second part crimping section and the compressive plane of the part crimping section of mould the 3rd
The axis direction of 12 cylindrical cavities that can be included from the part of mould first is put into；
The size of the cylindrical cavity 4 that the part of mould first is included is：Cylindrical bottom is the circle of a diameter of 60 mm, circle
A height of 35 mm of cylindricality.
Method for preparing catalyst described in the present embodiment, by above-mentioned raw materials and integral catalyzer mould, its
Preparation method is comprised the steps of：
Step one, prepare molding precursor；
Step 2, filling inclusion enclave；
Step 3, to inclusion enclave apply pressure；
Step 4, the roasting of the program of formed blocks.
The specific method of aforementioned four step is as follows：
Step one, prepare molding precursor；Specific method is as follows：
Take aluminum precursor, iron precursor, manganese precursor, the first additive, second additive of certain mass；Wherein aluminum precursor quality is 78
g；The ratio between molal quantity containing aluminium element is 0.030 in molal quantity and aluminum precursor containing ferro element in iron precursor, and conversion cost is implemented
Iron precursor in example（Iron chloride）Quality be 4.88 g；Contain aluminium element in molal quantity and aluminum precursor containing manganese element in manganese precursor
The ratio between molal quantity be 0.006, the manganese precursor in conversion cost implementation（Manganese sulfate）Quality be 0.9 g；Iron precursor and manganese
The ratio between molal quantity containing aluminium element is 0.036 in the total mole number and aluminum precursor of ferro element and manganese element in precursor（It is less than
0.18）；The quality of the first additive is 0.045 times of aluminum precursor quality, and the quality of the second additive is aluminum precursor quality
0.088 times；Five kinds of materials uniformly mix, and obtain mixed-powder；Acid solution is then poured slowly into mixed-powder, dough is formed
The quality of mixture, wherein acid solution is 0.95 times of aluminum precursor quality；Hand is first passed through, dough is mixed using banded extruder afterwards
Thing carries out kneading so that aluminum precursor therein, the first additive, the second additive, acid solution further uniformly mix, and forms one
The moulded pottery not yet put in a kiln to bake of individual appearance uniform, does not have obvious drop on moulded pottery not yet put in a kiln to bake；The moulded pottery not yet put in a kiln to bake referred to as molding precursor obtained by said mixture kneading.
Step 2, filling inclusion enclave；Specific method is as follows：
Molding precursor described in the step of taking certain mass one, its quality is 41.0 g；Take the supportive material of certain mass, its matter
Amount is 3.9 g, is 0.095 times of molding precursor quality；Molding precursor is filled into monoblock type together with supportive material to urge
Agent mould（Accompanying drawing 1）In the cylindrical cavity 4 that first part 1 is included（As marked shown in 14）；Filling rear support
Material is formed precursor parcel；Inclusion enclave is formed after molding precursor parcel supportive material；By the second part of mould crimping section 6
The both sides of the cylindrical cavity 4 included from the part of mould first respectively with the part crimping section 10 of mould the 3rd load；Load
Inclusion enclave material requested is not limited with the order for placing the part of mould second or the part of mould the 3rd；When mould the second part press section
In the cylindrical cavity 4 that compressive plane 8, the compressive plane 12 of the part crimping section of mould the 3rd and the part of mould first for dividing are included
Wall is collectively forming an airtight cavity, and above-mentioned inclusion enclave is enclosed in the airtight cavity（As shown at 14）, complete to load step.
Step 3, to inclusion enclave apply pressure；Specific method is as follows：
The integral catalyzer mould combination that inclusion enclave will be assembled is placed on a hydraulic press, mould the second part pressure-bearing
Partial pressure-bearing surface 9, the pressure-bearing surface 13 of the part pressure-bearing part of mould the 3rd are contacted with the applying press member of hydraulic press so that liquid
Press pressure applied can act on above-mentioned two pressure-bearing surface；The pressure size of applying is 1.4 MPa；Apply pressure time
It is 40 min；The molding precursor after being pressurized then is taken out from mould and obtains formed blocks.
Step 4, the roasting of the program of formed blocks；Specific method is as follows：
Operation is dried to formed blocks described in step 3, part volatility moisture is left formed blocks with other materials,
Until the dried quality of formed blocks is about 70% before drying；The present embodiment is using the drying side dried naturally in atmosphere
Method；Formed blocks are placed in a Muffle furnace with temperature programmed control function afterwards carry out heating roasting；The atmosphere of roasting is
Air；Temperature and time relation in program roasting includes three temperature controlling stages, is referred to as the first temperature control stage, second
Temperature control stage and the 3rd temperature control stage；First temperature control stage had an initial temperature, and its value is 60oC, with a termination
Temperature, its value is 650oC；First temperature control stage was 3.3 from initial temperature to final temperature average ramp rateoC/min；
The total time in the first temperature control stage is 3 h；Second temperature control stage had an initial temperature, and its value is 650oC, with one
Final temperature, its value is also 650oC；Second temperature control stage was 0 from initial temperature to final temperature average ramp rateoC/
min；It is 5 h that second temperature controls the total time in stage；3rd temperature control stage had an initial temperature, and its value is 650oC,
With a final temperature, its value is 30oC, the 3rd temperature control stage is from initial temperature to final temperature average ramp rate
For -0.7oC/min；The total time in the 3rd temperature control stage is 14 h.
Complete after step 4, formed blocks are converted into the enhanced integral alumina of final products, i.e. high-specific surface area
Load ferrimanganic binary catalyst；Preparation process is completed.
By the sign to above-mentioned final products, the enhanced monoblock type of the product of above-mentioned preparation method, i.e. high-specific surface area
Alumina load ferrimanganic binary catalyst, is also provided simultaneously with following product feature：
（1）The quality of single catalyst block is 13.6 g；
（2）The specific surface area of catalyst is 195 m2/g；
（3）The iron of catalyst, manganese element gross mass content are up to 3.9 %（Iron content 3.2%, containing manganese 0.7%）；
（4）The X-ray diffraction peak of integral alumina load ferrimanganic binary catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and
Without the SPECTROSCOPIC CHARACTERIZATION related to iron component or manganese component.
Above-mentioned（2）（3）（4）The feature of point, the result contribution not comprising supportive material.
It is above-mentioned（3）（4）2 points combine explanation, on the basis of with considerable active metal component load capacity, iron, manganese activity
Component has decentralization very high on microcosmic.See in principle, if the microscopic particles of metal component can be with 5 more than nm
Obtain its X-ray diffraction peak.The assay method of the specific surface area of integral alumina load ferrimanganic binary catalyst is foregoing
Low temperature nitrogen adsorption-desorption isothermal method；Tested by same sign, while it has also been found that, integral alumina load ferrimanganic two
First catalyst also has a large amount of nanoscale Jie view hole roads.
Embodiment two,
The present embodiment is a comparative example, in order to which in embodiment one, supportive material is catalyzed for monoblock type for checking
The mechanical strength humidification of agent.Specific practice is distinguished and is with embodiment one：
Step 2, filling inclusion enclave；Supportive material is not used；It is identical with embodiment one that other load process；Now inclusion enclave
In only molding precursor, and be free of supportive material.
Resulting product is referred to as " integral alumina load ferrimanganic binary catalyst " after completion step 4（It is labeled as
Product A）.By the product " enhanced integral alumina load ferrimanganic binary catalyst " of embodiment one（Labeled as product B）With
The product A of this example carries out mechanical strength comparing, and process is as follows：
By above-mentioned two product（Sheet cylinder）It is individually placed in approximately the same plane, then with a rigid board for ruler shape
Body is positioned on two products, and product is located at the lower section that ruler two breaks.Ruler top to be placed on a rigid block movement certain high afterwards
Degree, allows its free-falling to clash into ruler middle part so that the impulsive force that rigid block movement falls is acted on two products by ruler.
The height of rigid block movement is improved constantly, until at least one product occurs to crush.
Test result finds that product A ruptures prior to product B, and the mechanical strength for illustrating product B is higher than product A；Namely
Say, embodiments of the invention one have reached the enhanced effect of mechanical strength of monolithic substrate product.
Embodiment three,
Other are with embodiment one, difference：
Iron precursor：Ferric nitrate；
Manganese precursor：Manganese acetylacetonate；
First additive：Sesbania powder；
Second additive：Ethanol；
Step one, prepare molding precursor；Wherein in iron precursor in molal quantity and aluminum precursor containing ferro element containing aluminium element mole
The ratio between number is 0.030, the iron precursor in conversion cost implementation（Ferric nitrate, disregards crystallization water section）Quality be 7.3 g；Manganese
The ratio between molal quantity containing aluminium element is 0.015 in molal quantity and aluminum precursor containing manganese element in precursor, in conversion cost implementation
Manganese precursor（Manganese sulfate）Quality be 3.8 g；Before total mole number and aluminium of the iron precursor with ferro element in manganese precursor with manganese element
The ratio between molal quantity containing aluminium element is 0.045 in body（Less than 0.18）；
Step 2, filling inclusion enclave；Molding precursor described in the step of taking certain mass one, its quality is 36 g；Take certain mass
Supportive material, its quality is 5.0 g, is 0.14 times of molding precursor quality；
Step 4, the roasting of the program of formed blocks；The atmosphere being wherein calcined is purity oxygen；Wherein the first temperature control stage has one
Initial temperature, its value is 40oC, with a final temperature, its value is 350oC；First temperature control stage is from initial temperature to end
Only temperature-averaging rate of temperature change is 2.1oC/min；The total time in the first temperature control stage is 2.5 h；Second temperature control stage had
One initial temperature, its value is 350oC, with a final temperature, its value is 700oC；Second temperature control stage is from initial temperature
It is 1 to final temperature average ramp rateoC/min；It is 5.8 h that second temperature controls the total time in stage；3rd temperature control rank
Section has an initial temperature, and its value is 700oC, with a final temperature, its value is 30oC, the 3rd temperature control stage is from
Beginning temperature to final temperature average ramp rate be -0.55oC/min；The total time in the 3rd temperature control stage is 20.3 h.
Complete after step 4, formed blocks are converted into the enhanced integral alumina of final products, i.e. high-specific surface area
Load ferrimanganic binary catalyst；Preparation process is completed.
By the sign to above-mentioned final products, the enhanced monoblock type of the product of above-mentioned preparation method, i.e. high-specific surface area
Alumina load ferrimanganic binary catalyst, is also provided simultaneously with following product feature：
（1）The quality of single catalyst block is 15.9 g；
（2）The specific surface area of catalyst is 230 m2/g；
（3）The iron of catalyst, manganese element gross mass content are up to 4.7 %（The % of iron content 3.1, containing the % of manganese 1.6）；
（4）The X-ray diffraction peak of integral alumina load ferrimanganic binary catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and
Without the SPECTROSCOPIC CHARACTERIZATION related to iron component or manganese component.
Example IV,
Other are with embodiment one, difference：
Supportive material：Diameter is about the aluminum alloy sheet of 30 mm, and monolithic quality is about 1.1 g.
Using integral catalyzer mould, the cylindrical bottom of wherein cylindrical cavity 4 is a diameter of 100 mm
Circle, a height of 35 mm of cylinder.
Step 2, filling inclusion enclave；Molding precursor described in the step of taking certain mass one, its quality is 65.0 g；Take one
Determine the supportive material of quality, its quality is 5.6 g, be 0.086 times of molding precursor quality；
Step 3, to molding precursor apply pressure；The pressure size for wherein applying is 1.6 MPa；It is 1.5 to apply pressure time
h。
Complete after step 4, formed blocks are converted into the enhanced integral alumina of final products, i.e. high-specific surface area
Load ferrimanganic binary catalyst；Preparation process is completed.
By the sign to above-mentioned final products, the enhanced monoblock type of the product of above-mentioned preparation method, i.e. high-specific surface area
Alumina load ferrimanganic binary catalyst, is also provided simultaneously with following product feature：
（1）The quality of single catalyst block is 21.3 g；
（2）The specific surface area of catalyst is 190 m2/g；
（3）The iron of catalyst, manganese element gross mass content are up to 3.8 %（Iron content 3.1%, containing manganese 0.7%）；
（4）The X-ray diffraction peak of catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of the spectrum on ferrimanganic binary composition
Learn feature.
Claims (6)
1. a kind of high-specific surface area enhanced integral alumina load ferrimanganic binary catalyst, comprising method for preparing catalyst with
Catalyst prod feature, it is characterised in that wherein method for preparing catalyst uses the following raw material：
Aluminum precursor：One kind of aluminium hydroxide, boehmite, or above-mentioned substance arbitrary proportion mixture；
Iron precursor：Be frerrous chloride, iron chloride, ferrous nitrate, ferric nitrate, ferrous sulfate, ferric sulfate, ferrous acetate, ferric acetate,
Ferrous carbonate, ferric carbonate, iron hydroxide, ferrous oxalate, ferric oxalate, ferric acetyl acetonade, ferrocene, methyl ferrocene, ethyl two
One kind in luxuriant iron, ethylenediamine tetra-acetic acid-iron complex, or above-mentioned substance arbitrary proportion mixture；
Manganese precursor：It is manganese sulfate, manganese chloride, manganese nitrate, manganese carbonate, manganese acetylacetonate, sodium ethylene diamine tetracetate manganese, ethylenediamine tetraacetic
One kind in manganese acetate, manganese oxalate, or the mixture that above-mentioned substance is mixed with arbitrary proportion；
First additive：It is sesbania powder, sesbania gum, guar gum, cation guar gum, sodium alginate, carboxymethylcellulose calcium, carboxylic second
One kind in base cellulose, sodium carboxymethylcellulose, sodium hydroxyethlcellulose, galactomannans, or above-mentioned substance is any
The mixture of ratio；
Second additive：Be ethanol, propyl alcohol, butanol, ethylene glycol, propane diols, polyethylene glycol, polyvinyl alcohol, glucose, fructose,
Sucrose, maltose, cellobiose, granularity are less than the carbon black of 60 mesh, granularity less than the one kind in the water soluble starch of 60 mesh,
Or the mixture of above-mentioned substance arbitrary proportion；
Acid solution：A kind of aqueous solution, contains nitric acid, sulfuric acid, hydrochloric acid, acetic acid, oxalic acid, phosphoric acid, citric acid, maleic acid, tartaric acid
In one or more materials, the pH value of the aqueous solution is in the range of 0.0 ~ 4.0；
Supportive material：One kind in wire, bonding jumper, sheet metal, wire netting or carbon fiber, or the above-mentioned type material
It is applied in combination with arbitrary proportion；The material of wherein metal be ferrimanganic binary, stainless steel, ferrimanganic binary, chromium, ferrimanganic binary, zinc,
A kind of or based on above-mentioned material alloy material in aluminium, titanium, manganese；Metal material species can be one kind of above-mentioned material,
Or various be applied in combination with arbitrary proportion；For wire, bonding jumper or carbon fiber, its stretched length is not less than 1 cm；
For sheet metal or wire netting, its circumference projected area is not less than 0.1 cm2；
Above-mentioned method for preparing catalyst, uses integral catalyzer mould；The mould includes the part of mould first, mould
Have the second part and the part of mould the 3rd；The part of mould first includes a cylindrical cavity；The part of mould second includes mould
Second part crimping section and mould the second part pressure-bearing part；The geometry of mould the second part crimping section is cylinder
Body, it has a compressive plane, and the geometry of the compressive plane is circle；Mould the second part pressure-bearing part has a pressure-bearing
Face；The part of mould the 3rd includes the part crimping section of mould the 3rd and the part pressure-bearing part of mould the 3rd；The part of mould the 3rd is squeezed
The geometry of laminate section is cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；Mould the 3rd 0
Part pressure-bearing part has a pressure-bearing surface；The compressive plane of mould the second part crimping section and the part crimping section of mould the 3rd
The axis direction of the cylindrical cavity that compressive plane can be included from the part of mould first is put into；
Above-mentioned method for preparing catalyst, by above-mentioned raw materials and integral catalyzer mould, its preparation method include with
Lower step：
Step one, prepare molding precursor；
Step 2, filling inclusion enclave；
Step 3, to inclusion enclave apply pressure；
Step 4, the roasting of the program of formed blocks.
2. the enhanced integral alumina of high-specific surface area according to claim 1 loads ferrimanganic binary catalyst, and it is special
Levy and be, the step one in its preparation method（Prepare molding precursor）Specific method it is as follows：Take aluminum precursor, the iron of certain mass
Precursor, manganese precursor, the first additive, the second additive；Contain aluminium in molal quantity and aluminum precursor containing ferro element wherein in iron precursor
The ratio between molal quantity of element is 0.003 ~ 0.12；Molal quantity in manganese precursor containing manganese element and rubbing containing aluminium element in aluminum precursor
The ratio between your number is 0.003 ~ 0.12；Iron precursor contains aluminium in the total mole number and aluminum precursor with ferro element in manganese precursor with manganese element
The ratio between molal quantity of element is less than 0.18；The quality of the first additive is 0.01 ~ 0.1 times of aluminum precursor quality；Second addition
The quality of thing is 0 ~ 0.2 times of aluminum precursor quality；Five kinds of materials uniformly mix, and obtain mixed-powder；Then acid solution is delayed
It is slow to pour into mixed-powder, dough is formed, the quality of wherein acid solution is 0.5 ~ 1.3 times of aluminum precursor quality；Pass through
Hand or banded extruder carry out kneading to dough so that aluminum precursor therein, the first additive, the second additive, acid
Solution further uniformly mixes, and forms a moulded pottery not yet put in a kiln to bake, does not have obvious drop on moulded pottery not yet put in a kiln to bake；The mud obtained by said mixture kneading
Base is referred to as molding precursor.
3. the enhanced integral alumina of high-specific surface area according to claim 1 loads ferrimanganic binary catalyst, and it is special
Levy and be, the step two in its preparation method（Load inclusion enclave）Specific method it is as follows：Described in the step of taking certain mass one
Molding precursor, its quality is in the range of 2 ~ 400g；The supportive material of certain mass is taken, its quality is molding precursor quality
0.01 ~ 0.6 times；Molding precursor is filled into the part of integral catalyzer mould first together with supportive material to be wrapped
In the cylindrical cavity for containing；Filling rear support material is formed precursor parcel；Formed after molding precursor parcel supportive material
Inclusion enclave；Mould the second part crimping section and the part crimping section of mould the 3rd are included from the part of mould first respectively
The both sides of cylindrical cavity load；Load inclusion enclave material requested and place the order of the part of mould second or the part of mould the 3rd
Do not limit；Compressive plane, the compressive plane and mould the 1st of the part crimping section of mould the 3rd when mould the second part crimping section
The cylindrical empty cavity wall that part is included is collectively forming an airtight cavity, and above-mentioned inclusion enclave is enclosed in the airtight cavity,
Complete to load step.
4. the enhanced integral alumina of high-specific surface area according to claim 1 loads ferrimanganic binary catalyst, and it is special
Levy and be, the step three in its preparation method（Pressure is applied to inclusion enclave）Specific method it is as follows：Inclusion enclave will be assembled
The combination of integral catalyzer mould is placed on a hydraulic press, the pressure-bearing surface of mould the second part pressure-bearing part, mould the
The pressure-bearing surface of three part pressure-bearing parts is contacted with the applying press member of hydraulic press so that hydraulic press pressure applied can be made
For above-mentioned two pressure-bearing surface；The pressure size of applying is in the range of 0.1 ~ 5 MPa；Apply pressure time in 20 s ~ 4 h
In the range of；The molding precursor after being pressurized then is taken out from mould and obtains formed blocks.
5. the enhanced integral alumina of high-specific surface area according to claim 1 loads ferrimanganic binary catalyst, and it is special
Levy and be, the step four in its preparation method（The program roasting of formed blocks）Specific method it is as follows：To described in step 3 into
Type block is dried operation, part volatility moisture is left formed blocks with other materials, until after formed blocks are dried
Quality be dry before less than 85%；Drying process including but not limited to drying in atmosphere, drying in baking oven or Muffle furnace,
Dried in vacuum drying chamber, dried in drier, blowing drying, daylight is dried, infrared lamp dry, centrifuge is dried etc. operates,
Or any combination operation of aforesaid operations；Formed blocks are placed in a heater with temperature programmed control function afterwards carried out
Roasting；The atmosphere of roasting is air, or purity oxygen, or any mixed gas of the oxygenous ratio more than 20%；In program roasting
Temperature and time relation includes three temperature controlling stages, is referred to as the first temperature control stage, the second temperature control stage and the 3rd temperature
The control stage；First temperature control stage had an initial temperature, and its value is 20 ~ 150oCertain value in the range of C, with one
Final temperature, its value is 300 ~ 750oCertain value in the range of C；First temperature control stage put down from initial temperature to final temperature
Equal rate of temperature change is 0.5 ~ 8oIn the range of C/min；The total time of the first temperature controlling stages is in 30 min ~ 12 h models
In enclosing；Second temperature control stage had an initial temperature, and its value is 300 ~ 750oCertain value in the range of C, with an end
Only temperature, its value is also 300 ~ 750oCertain value in the range of C；Second temperature control stage put down from initial temperature to final temperature
Equal rate of temperature change is -2 ~ 2oIn the range of C/min；The total time in the second temperature control stage is in the range of 1 ~ 6 h；3rd temperature
The control stage has an initial temperature, and its value is 300 ~ 750oCertain value in the range of C, with a final temperature, its value
It is 20 ~ 150oCertain value in the range of C；3rd temperature control stage from initial temperature to final temperature average ramp rate-
8 ~ -0.5 oIn the range of C/min；The total time in the 3rd temperature control stage is in the range of 2 ~ 24 h；
Complete after step 4, formed blocks are converted into the enhanced integral alumina load of final products, i.e. high-specific surface area
Ferrimanganic binary catalyst；Preparation process is completed.
6. the enhanced integral alumina load ferrimanganic binary catalyst of high-specific surface area according to claim 1-5 and
Its preparation method, it is characterised in that the enhanced integral alumina load iron of the product of above-mentioned preparation method, i.e. high-specific surface area
Manganese binary catalyst, is also provided simultaneously with following product feature：（1）The quality of single catalyst block is up to 1 ~ 100 g；（2）
The overall specific surface area of catalyst is 150 ~ 550 m2/g；（3）The iron of catalyst, manganese element gross mass content up to 0.6 ~
20 %；（4）The X-ray diffraction peak of catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of and iron component or manganese component phase
The SPECTROSCOPIC CHARACTERIZATION of pass.
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Application publication date: 20170524 |