CN106732468A - A kind of high-specific surface area integral alumina carrier - Google Patents
A kind of high-specific surface area integral alumina carrier Download PDFInfo
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- CN106732468A CN106732468A CN201710040246.5A CN201710040246A CN106732468A CN 106732468 A CN106732468 A CN 106732468A CN 201710040246 A CN201710040246 A CN 201710040246A CN 106732468 A CN106732468 A CN 106732468A
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- 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 83
- 239000002243 precursor Substances 0.000 claims abstract description 58
- 238000000465 moulding Methods 0.000 claims abstract description 55
- 238000002360 preparation method Methods 0.000 claims abstract description 54
- 239000000654 additive Substances 0.000 claims abstract description 37
- 230000000996 additive effect Effects 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000002788 crimping Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 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
- 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
- 239000000665 guar gum Substances 0.000 claims description 4
- 235000010417 guar gum Nutrition 0.000 claims description 4
- 229960002154 guar gum Drugs 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
- 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 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
- 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
- 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
- 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
- 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
- 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
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 21
- 238000005516 engineering process Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 10
- 241000219782 Sesbania Species 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920001410 Microfiber Polymers 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003245 coal Substances 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
- 239000010949 copper Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 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
- 239000011343 solid material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B01J35/615—
-
- B01J35/647—
Abstract
The invention belongs to be catalyzed with adsorption technology field, be related to one kind by alumina precursor moulded pottery not yet put in a kiln to bake one-shot forming to be with high-specific surface area monolithic substrate and preparation method thereof.Its technical scheme is to use the following raw material：Silicon source, the first additive, the second additive, acid solution；Use monolithic substrate mould；By above-mentioned raw materials and monolithic substrate mould, its preparation process is comprised the steps of：Step one, prepare molding precursor；The assembling of step 2, molding precursor and mould；Step 3, to molding precursor apply pressure；Step 4, the roasting of the program of formed blocks.Its good effect is to may be up to 600 m by the specific surface area of the integral alumina carrier obtained by above-mentioned preparation method2/g；Preparation process is simple, is suitable for large-scale production；One-shot forming reduces processing step number；It is easy to be docked with follow-up active metal component load step；Separation costs are saved for subsequent catalyst, absorption production establish important foundation.
Description
Technical field
The invention belongs to be catalyzed with adsorption technology field, be related to a kind of integral alumina carrier and preparation method thereof, have
Body ground, is related to one kind to be with high-specific surface area monolithic substrate and preparation method thereof by alumina precursor moulded pottery not yet put in a kiln to bake one-shot forming.
Background technology
In chemical products, production of energy and field of environment protection, all to be related in chemical reaction process, catalyst is most heavy
One of material wanted.Solid catalyst is most common catalyst mode.From principle, in order to increase solid catalyst with it is anti-
The contact area between thing is answered, it is necessary to improve the surface area of solid catalyst.Therefore, by the active component with catalysis activity
（Transition metal component is most commonly seen）It is the normal of making solid catalyst to load on the porous material with high-specific surface area
Square method.In this area, the material for carrying active component is referred to as catalyst carrier, or referred to as carrier, has loaded catalysis activity
Catalyst after component is referred to as loaded catalyst.Common high specific surface carrier is generally graininess or powdered, such as living
Property charcoal, molecular sieve, porous aluminum oxide etc..It is decided by the macroscopic form of carrier due to catalyst macroscopic form；Therefore with porous
The catalyst that property particle or powder are prepared as carrier, its macroscopic form is also porous particles or powder；With monolithic substrate
Used as catalyst prepared by carrier, i.e. integral catalyzer, its macroscopic form is the larger block of a volume.Monoblock type is catalyzed
With particle or powder catalyst morphological differences substantially, in actual use, integral catalyzer is with a whole larger block for agent
Form occur, it has some clear advantages compared with the latter：Such as its catalyst filling and more convenient, the Qian Zheke of recovery
Substantially reduce the separation costs of running cost or catalyst-product；For in fixed bed reactors, the former often to have smaller
Pressure drop；The former high mechanical strength, deformation is small, safer in actual production use.
Because catalysis and adsorption process have certain similitude, porous material load active component is also commonly used for absorption
Process.Related product can be described as load type adsorbing agent, and it is also more common in production of energy, environmental protection.Equally, with particle or
Powdered substance is also particle or powdered as the adsorbent macroscopic form that carrier is obtained；Using monolithic substrate as carrier system
Standby adsorbent, i.e. monoblock type adsorbent, its macroscopic form are the larger blocks of a volume.
As previously described, because the macroscopic form of carrier determines the macroscopic form of final catalyst or adsorbent product, because
In the preparation of integral catalyzer or adsorbent, how to prepare monolithic substrate is a key technology for this.Aluminum oxide is work
One of the most frequently used carrier in industry application and laboratory research, but this area also lacks on high-ratio surface monoblock type oxygen at present
Change the preparation method of alumina supporter, especially the one-shot forming preparation method of oxidized alumina supporter.It is related to use monoblock type at present
The catalyst method of alumina support, be all mostly be molded block be ground, for example cordierite be ground, carry out Alumina gel
Deng the full-filling of alumina precursor.By the document of the reports such as Henan coal industry Chemical Group research institute seedling outstanding person【Macroporous structure is preferential to CO
Oxidation monoblock type CuO-CeO2/α-Al2O3The influence of catalysis activity, petrochemical industry, volume 2011,40,9 phases, page 932】In describe
A kind of preparation method of the copper-based integral catalyzer of alumina load.For the preparation of carrying alumina body portion, the method passes through
Water-oil phase prepares polystyrene emulsion and then aggregates into polystyrene moulding, and Alumina gel is filled into polystyrene moulding afterwards
In, by 1300oC high-temperature roastings removing template obtains alumina support.Then finally it is catalyzed by equi-volume impregnating
Agent.The total production procedure of the method is more complicated, and flow is more long.Meanwhile, the document is not disclosed in terms of specific surface area
Data.From principle, by 1300oα-the Al that C high-temperature roastings are obtained2O3Carrier surface area is smaller.Patent CN1411391A
Disclose a kind of integral catalyzer preparation method being made up of metal microfibre and catalyst granules.It is a certain amount of in the invention
Metal microfibre be sintered into rigid tridimensional network, network structure has fettered the catalyst granules of the inside.The catalysis
Agent has the advantages that high stability, superior thermal conductivity, long service life.But its matrix is defined in metal fento, may limit
The expansion application of the method processed.Catalyst granules is limited in net inside also can to a certain extent sacrifice catalyst with reactant
Contact area.Meanwhile, the invention does not disclose relevant surfaces volume data yet can be used as reference.
Therefore for the preparation of integral catalyzer or monolithic substrate, also there is this improvement preparation side in this area
The technical need of method, especially prepares the demand of the process simple and easy to apply of high-specific surface area monolithic substrate.
The content of the invention
In order to overcome the problems of prior art, the present invention to propose a kind of first making alumina precursor moulded pottery not yet put in a kiln to bake, and
By mould compression forming, the technology path of product is then obtained by the roasting of fine program.Can by the technology path
With obtain high-specific surface area, it is microcosmic on possess the integral alumina carrier in nanoscale duct；The preparation method need not be high simultaneously
Your equipment, raw material sources are simple, more friendly environment, safe operation, cost are relatively low.
Realizing the concrete technical scheme of above-mentioned technology path is：
A kind of high-specific surface area integral alumina carrier, comprising integral alumina support preparation method and integral alumina
Vector product feature；Wherein preparation method uses the following raw material：
Silicon source：The one kind in aluminium hydroxide, boehmite, aluminum nitrate, or above-mentioned substance arbitrary proportion mixture；
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.
The preparation method of above-mentioned integral alumina carrier, uses monolithic substrate mould；The mould includes
The part of mould first, the part of mould second and the part of mould the 3rd；The part of mould first includes a cylindrical cavity；Mould
Two parts include mould the second part crimping section and mould the second part pressure-bearing part；Mould the second part crimping section it is several
What is shaped as cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；Mould the second part pressure-bearing part
With a pressure-bearing 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；Mould
Has the geometry of the 3rd part crimping section for cylinder, it has a compressive plane, and the geometry of the compressive plane is circle
Shape；The part pressure-bearing part of mould the 3rd has a pressure-bearing surface；The compressive plane of mould the second part crimping section and mould the 3rd
The axis direction of the cylindrical cavity that the compressive plane of part crimping section can be included from the part of mould first is put into.
The preparation method of above-mentioned integral alumina carrier, by above-mentioned raw materials and monolithic substrate mould, its
Preparation process is comprised the steps of：
Step one, prepare molding precursor；
The assembling of step 2, molding precursor and mould；
Step 3, to molding precursor 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：
Silicon source, the first additive, second additive of certain mass are taken, wherein the quality of the first additive is silicon source quality
0.01 ~ 0.1 times, the quality of the second additive is 0 ~ 0.2 times of silicon source quality；Three kinds of materials uniformly mix, and obtain mixed powder
End；Acid solution is then poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is silicon source quality
0.5 ~ 1.3 times；Kneading is carried out to dough by hand or banded extruder so that silicon source therein, the first additive,
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；By above-mentioned mixing
The moulded pottery not yet put in a kiln to bake that thing kneading is obtained referred to as molding precursor.
The assembling of step 2, molding precursor and mould；Specific method is as follows：
Molding precursor is filled in the cylindrical cavity that the part of mould first of monolithic substrate mould is included, is molded
The quality of precursor is in 2 ~ 400 g ranges；Mould the second part crimping section and the part crimping section of mould the 3rd are distinguished
The both sides of the cylindrical cavity included from the part of mould first are put into；Load molding precursor material requested and place mould second
The order of part or the part of mould the 3rd is not limited；Compressive plane, the part of mould the 3rd extruding when mould the second part crimping section
Partial compressive plane is collectively forming an airtight cavity with the cylindrical empty cavity wall that the part of mould first is included, and will be above-mentioned
Molding precursor is enclosed in the airtight cavity, completes to load step.
Step 3, to molding precursor apply pressure；Specific method is as follows：
The molding precursor that will be assembled is combined with monolithic substrate mould and is placed on a hydraulic press, and the part of mould second holds
The pressure-bearing surface of laminate section, 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 liquid
Press 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
The plus-pressure time is in the range of 20 s ~ 4 h；Then it is removed from the molds the molding precursor after being pressurized 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 75% 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 final products integral alumina carrier；Preparation process is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, high-ratio surface integral alumina carrier,
Also it is provided simultaneously with following characteristics：
（1）The block quality of single integral alumina carrier is up to 1 ~ 100 g；
（2）The specific surface area of integral alumina carrier is 150 ~ 600 m2/g。
It is noted that the characterization test method of the present invention and non-protected product, but the product obtained by the protection present invention
Due feature.Characterization test method used by this product is all method that those skilled in the art commonly use.
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 75% 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）The preparation process is simple of integral alumina carrier, raw material are cheap, and running cost is low, are suitable for large-scale production；
The part of monolithic substrate mould second of the invention or the 3rd part can be used for formed blocks after molding precursor pressure
The demoulding so that operation it is easier.
（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）Compared with the existing monoblock type ground of most of utilizations then coats catalytic component, one-shot forming reduces work
Skill number of steps；Whole block is all alumina support simultaneously, and more active metal components can be loaded when subsequently using.
（4）Common monolithic substrate totality specific surface area is relatively low（Often it is less than<20 m2/g）, and monoblock type of the invention
The specific surface area of alumina support may be up to 600 m2/g.This is an important advance of the invention.Product also has substantial amounts of
Nanoscale Jie's view hole road, size makes it have good catalysis, adsorption applications prospect between 6 ~ 20 nm.
（5）It is easy to be docked with follow-up active metal component load step, can further prepares active metal component
Integral catalyzer.For common pellet type catalyst or catalyst carrier, product of the present invention can be as one
Individual entirety is used, be subsequent catalyst, absorption production save separation costs establish important foundation.
Brief description of the drawings
The monolithic substrate mould schematic diagram of accompanying drawing 1.；1 is the part of mould first；2 is the part of mould second；3 is mould
Has the 3rd part；4 is the cylindrical cavity that the part of mould first is included；5 be the part of mould first institute comprising cylindrical cavity 4
Geometrical axis, the axis only to facilitate understand and draw, and non-actual existence；6 is mould the second part crimping section；
7 is mould the second part pressure-bearing part；8 is the compressive plane of mould the second part crimping section；9 is mould the second part pressure-bearing portion
The pressure-bearing surface for dividing；10 is the part crimping section of mould the 3rd；11 is the part pressure-bearing part of mould the 3rd；12 is the part of mould the 3rd
The compressive plane of 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 and are included
Cylindrical cavity 4 inside molding precursor；8th, 9,12,13 4 directions of arrow are also represented when mould is integrally squeezed by external force
After pressure, the Impact direction of mould is illustrated.
Specific embodiment
Embodiment one,
A kind of high-specific surface area integral alumina carrier, comprising integral alumina support preparation method and integral alumina
Vector product feature；Wherein preparation method uses the following raw material：
Silicon source：Aluminium hydroxide；
First additive：The mixture of sesbania powder and sodium hydroxyethlcellulose, the two mass ratio is 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；
The preparation method of the integral alumina carrier described in the present embodiment, uses monolithic substrate mould；The shaping mould
During tool work 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；
The part of mould first includes a cylindrical cavity 4；The second part of mould 2 includes the second part of mould crimping section 6 and mould
Second 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 geometry of the compressive plane 8 is circle；Mould the second part pressure-bearing part 7 has a pressure-bearing surface 9；The part 3 of mould the 3rd
Comprising the part crimping section 10 of mould the 3rd and the part pressure-bearing part 11 of mould the 3rd；The part crimping section 10 of mould the 3rd it is several
What is shaped as cylinder, and it has a compressive plane 12, and the geometry of the compressive plane 12 is circle；The part pressure-bearing of mould the 3rd
Part 11 has a pressure-bearing surface 13；The compressive plane 8 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 12 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.
The preparation method of the integral alumina carrier described in the present embodiment, by above-mentioned raw materials and monolithic substrate into
Pattern has, and its preparation process is comprised the steps of：
Step one, prepare molding precursor；
The assembling of step 2, molding precursor and mould；
Step 3, to molding precursor 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：
Silicon source, the first additive, second additive of certain mass are taken, wherein silicon source quality is 100 g, wherein the first additive
Quality be 0.05 times of silicon source quality, the quality of the second additive is 0.08 times of silicon source quality；Three kinds of materials uniformly mix,
Obtain mixed-powder；Acid solution is then poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is
0.85 times of silicon source quality；Hand is first passed through, kneading is carried out to dough using banded extruder afterwards so that silicon source therein,
First additive, the second additive, acid solution further uniformly mix, and form a moulded pottery not yet put in a kiln to bake for appearance uniform, do not have on moulded pottery not yet put in a kiln to bake
Obvious drop；The moulded pottery not yet put in a kiln to bake referred to as molding precursor obtained by said mixture kneading.
The assembling of step 2, molding precursor and mould；Specific method is as follows：
Molding precursor is filled in the cylindrical cavity 4 that first part of mould 1 of monolithic substrate mould is included, such as
Shown in the mark 14 of accompanying drawing 1；The quality of molding precursor is 13.5 g；And by the second part of mould crimping section 6 and mould the 3rd
The both sides of the cylindrical cavity 4 that part crimping section 10 is included from the part of mould first respectively are put into；Load molding precursor institute
Material is needed not limited with the order for placing the part of mould second or the part of mould the 3rd；When the extruding of mould the second part crimping section
The common shape of inwall of cylindrical cavity 4 that face 8, the compressive plane 12 of the part crimping section of mould the 3rd are included with the part of mould first
Into an airtight cavity, and above-mentioned molding precursor is enclosed in the airtight cavity（As shown at 14）, complete to load step.
Step 3, to molding precursor apply pressure；Specific method is as follows：
The molding precursor that will be assembled is combined with monolithic substrate mould and is placed on a hydraulic press, and the part of mould second holds
The pressure-bearing surface 9 of laminate section is contacted with the pressure-bearing surface 13 of the part pressure-bearing part of mould the 3rd with the applying press member of hydraulic press, is made
Obtaining hydraulic press pressure applied can act on above-mentioned two pressure-bearing surface；The pressure size of applying is 1 MPa；When applying pressure
Between be 8 min；Then it is removed from the molds the molding precursor after being pressurized 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 63% 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 3.0 h；Second temperature control stage had an initial temperature, and its value is 650oC, with one
Individual 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 final products integral alumina carrier；Preparation process is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, high-ratio surface integral alumina carrier,
Also it is provided simultaneously with following characteristics：
（1）The quality of single integral alumina carrier is up to 3.2 g；
（2）The specific surface area of integral alumina carrier is 228 m2/g。
The assay method of the specific surface area of alumina support is foregoing low temperature nitrogen adsorption-desorption isothermal method；Pass through
It is same to characterize experiment, while it has also been found that, integral alumina carrier also has a large amount of nanoscale Jie view hole roads, its bore dia average
About 12 nm.
Embodiment two,
Other are with embodiment one, difference：
First additive：Sesbania powder；
Second additive：Ethanol；
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 19.0 g.
Complete after step 4, formed blocks are converted into final products integral alumina carrier；Preparation process is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, high-ratio surface integral alumina carrier,
Also it is provided simultaneously with following characteristics：
（1）The quality of single integral alumina carrier is up to 5.5 g；
（2）The specific surface area of integral alumina carrier is 245 m2/g。
Also found simultaneously, integral alumina carrier also has a large amount of nanoscale Jie view hole roads, its bore dia average is about 7
nm。
Embodiment three,
Other are with embodiment one, difference：
Using monolithic substrate mould, the cylindrical bottom of wherein cylindrical cavity 4 is the circle of a diameter of 100 mm, circle
A height of 35 mm of cylindricality.
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 52.2 g.
Complete after step 4, formed blocks are converted into final products integral alumina carrier；Preparation process is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, high-ratio surface integral alumina carrier,
Also it is provided simultaneously with following characteristics：
（1）The quality of single integral alumina carrier is up to 11.3 g；
（2）The specific surface area of integral alumina carrier is 203 m2/g。
Example IV,
Other are with embodiment one, difference：
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 final products integral alumina carrier；Preparation process is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, high-ratio surface integral alumina carrier,
Also it is provided simultaneously with following characteristics：
（1）The quality of single integral alumina carrier is up to 3.6 g；
（2）The specific surface area of integral alumina carrier is 229 m2/g。
Also found simultaneously, integral alumina carrier also has a large amount of nanoscale Jie view hole roads, its bore dia average is about
11 ~12 nm。
Embodiment five,
Other are with embodiment one, difference：
First additive：Sesbania powder；
Second additive：Ethanol；
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 20.1 g.
By the sign to obtained integral alumina carrier, integral alumina carrier also has the characteristics that：
Step 3, to molding precursor apply pressure；The pressure size for wherein applying is 1.5 MPa；Applying pressure time is 2 h.
Complete after step 4, formed blocks are converted into final products integral alumina carrier；Preparation process is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, high-ratio surface integral alumina carrier,
Also it is provided simultaneously with following characteristics：
（1）The quality of single integral alumina carrier is up to 5.6 g；
（2）The specific surface area of integral alumina carrier is 236 m2/g。
Embodiment six,
Other are with embodiment one, difference：
First additive：Sesbania powder；
Second additive：Ethylene glycol；
Acid solution：Aqueous solution of nitric acid, its pH value is 0.3.
Step one, prepare molding precursor；Specific method is as follows：
Silicon source, the first additive, second additive of certain mass are taken, wherein the quality of the first additive is silicon source quality
0.02 times, the quality of the second additive is 0.02 times of silicon source quality；Three kinds of materials uniformly mix, and obtain mixed-powder；Then
Acid solution is poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is 0.9 times of silicon source quality.
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 20.0 g.
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
It is 2.1 to final temperature average ramp rateoC/min；The total time in the first temperature control stage is 2.5 h；Second temperature control stage
With an initial temperature, its value is 350oC, with a final temperature, its value is 700oC；Second temperature control stage is from starting
Temperature to final temperature average ramp rate be 1oC/min；It is 5.8 h that second temperature controls the total time in stage；3rd temperature
The control stage has an initial temperature, and its value is 700oC, with a final temperature, its value is 30oC, the 3rd temperature control stage
It is -0.55 from initial temperature to final temperature average ramp rateoC/min；The total time in the 3rd temperature control stage is 20.3
h。
Complete after step 4, formed blocks are converted into final products integral alumina carrier；Preparation process is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, high-ratio surface integral alumina carrier,
Also it is provided simultaneously with following characteristics：
（1）The quality of single integral alumina carrier is up to 5.8 g；
（2）The specific surface area of integral alumina carrier is 259 m2/g。
Claims (6)
1. a kind of high-specific surface area integral alumina carrier, comprising integral alumina carrier its preparation method and monoblock type oxygen
Change the product feature of alumina supporter, it is characterised in that wherein preparation method uses the following raw material：
Silicon source：The one kind in aluminium hydroxide, boehmite, aluminum nitrate, or above-mentioned substance arbitrary proportion mixture；
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；
The preparation method of above-mentioned integral alumina carrier, it is characterised in that preparation process uses monolithic substrate mould；
The mould includes the part of mould first, the part of mould second and the part of mould the 3rd；The part of mould first includes a circle
Cylindrical cavity；The part of mould second includes mould the second part crimping section and mould the second part pressure-bearing part；Mould second
The geometry of part crimping section is cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；Mould
Second part pressure-bearing part has a pressure-bearing surface；The part of mould the 3rd includes the part crimping section of mould the 3rd and mould the 3rd
Part pressure-bearing part；The geometry of the part crimping section of mould the 3rd is cylinder, and it has a compressive plane, the compressive plane
Geometry for circle；The part pressure-bearing part of mould the 3rd has a pressure-bearing surface；Mould the second part crimping section squeeze
The axis side of the cylindrical cavity that pressure surface can be included with the compressive plane of the part crimping section of mould the 3rd from the part of mould first
To being put into；
The preparation method of above-mentioned integral alumina carrier, it is characterised in that be molded by above-mentioned raw materials and monolithic substrate
Mould, its preparation process is comprised the steps of：
Step one, prepare molding precursor；
The assembling of step 2, molding precursor and mould；
Step 3, to molding precursor apply pressure；
Step 4, the roasting of the program of formed blocks.
2. a kind of high-specific surface area integral alumina carrier according to claim 1, it is characterised in that wherein overall
Formula carrying alumina preparation step one（Prepare molding precursor）Specific method it is as follows：Take silicon source, first of certain mass
Additive, the second additive, wherein the quality of the first additive is 0.01 ~ 0.1 times of silicon source quality, the quality of the second additive
It is 0 ~ 0.2 times of silicon source quality；Three kinds of materials uniformly mix, and obtain mixed-powder；Acid solution is then poured slowly into mixed powder
End, forms dough, and the quality of wherein acid solution is 0.5 ~ 1.3 times of silicon source quality；By hand or banded extruder pair
Dough carries out kneading so that silicon source therein, the first additive, the second additive, acid solution are further uniformly mixed
Close, form a moulded pottery not yet put in a kiln to bake, there is no 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.
3. a kind of high-specific surface area integral alumina carrier according to claim 1, it is characterised in that wherein overall
Formula carrying alumina preparation step 2（The assembling of molding precursor and mould）Specific method is as follows：Molding precursor is filled out
In the cylindrical cavity that the part of mould first loaded on monolithic substrate mould is included, the quality of molding precursor 2 ~
In 400 g ranges；By mould the second part crimping section and the part crimping section of mould the 3rd respectively from the first part of mould institute
Comprising the both sides of cylindrical cavity be put into；Load molding precursor material requested and place the part of mould second or mould the 3rd 0
The order of part is not limited；Compressive plane, the compressive plane and mould of the part crimping section of mould the 3rd when mould the second part crimping section
Have the cylindrical empty cavity wall that the first part included and be collectively forming an airtight cavity, and it is close that above-mentioned molding precursor is enclosed in into this
In closed chamber body, complete to load step.
4. a kind of high-specific surface area integral alumina carrier according to claim 1, it is characterised in that wherein monoblock type
Carrying alumina preparation step 3（Pressure is applied to molding precursor）Specific method is as follows：The molding precursor that to assemble with
The combination of monolithic substrate mould is placed on a hydraulic press, pressure-bearing surface, the mould the 3rd of mould the second part pressure-bearing part
The pressure-bearing surface of part pressure-bearing part is contacted with the applying press member of hydraulic press so that hydraulic press pressure applied can be acted on
In 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 models
In enclosing；Then it is removed from the molds the molding precursor after being pressurized and obtains formed blocks.
5. according to a kind of high-specific surface area integral alumina carrier described in claim 1, it is characterised in that wherein monoblock type oxygen
Change alumina supporter preparation method step 4 (the program roastings of formed blocks) specific method as follows：Formed blocks described in step 3 are entered
Row drying process, makes part volatility moisture leave formed blocks with other materials, until the dried quality of formed blocks is
Before drying less than 75%；Drying process including but not limited to drying in atmosphere, drying, vacuum drying in baking oven or Muffle furnace
Dried in case, dried in drier, blowing drying, daylight is dried, infrared lamp dry, centrifuge is dried etc. operates, or above-mentioned behaviour
Any combination operation of work；Formed blocks are placed in a heater with temperature programmed control function are afterwards calcined；Roasting
The atmosphere of burning is air, or purity oxygen, or any mixed gas of the oxygenous ratio more than 20%；Program roasting in temperature with
Time relationship includes three temperature controlling stages, is referred to as the first temperature control stage, the second temperature control stage and the 3rd temperature control stage；
First temperature control stage had an initial temperature, and its value is 20 ~ 150oCertain value in the range of C, temperature is terminated with one
Degree, its value is 300 ~ 750oCertain value in the range of C；First temperature control stage is from initial temperature to final temperature mean temperature
Rate of change is 0.5 ~ 8oIn the range of C/min；The total time of the first temperature controlling stages is in the range of 30 min ~ 12 h；The
Two temperature control stages had an initial temperature, and its value is 300 ~ 750oCertain value in the range of C, with a final temperature,
Its value is also 300 ~ 750oCertain value in the range of C；Second temperature control stage became from initial temperature to final temperature mean temperature
Rate 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 control stage had
There is an initial temperature, its value is 300 ~ 750oCertain value in the range of C, with a final temperature, its value is 20 ~
150 oCertain 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 final products integral alumina carrier；Preparation process is completed.
6. a kind of high-specific surface area integral alumina carrier according to claim 1, it is characterised in that by entirety
The integral alumina vector product that formula carrying alumina preparation is obtained, its product feature is that single monoblock type is aoxidized
The block quality of alumina supporter is up to 1 ~ 100 g；The specific surface area of integral alumina carrier is 150 ~ 600 m simultaneously2/g。
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