CN106994361B - A kind of alumina support and preparation method with macroporous structure - Google Patents
A kind of alumina support and preparation method with macroporous structure Download PDFInfo
- Publication number
- CN106994361B CN106994361B CN201710409026.5A CN201710409026A CN106994361B CN 106994361 B CN106994361 B CN 106994361B CN 201710409026 A CN201710409026 A CN 201710409026A CN 106994361 B CN106994361 B CN 106994361B
- Authority
- CN
- China
- Prior art keywords
- alumina support
- macroporous structure
- acid
- chitosan
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 219
- 238000002360 preparation method Methods 0.000 title claims description 45
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011777 magnesium Substances 0.000 claims abstract description 27
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 239000002671 adjuvant Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 63
- 229920001661 Chitosan Polymers 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 41
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 25
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 21
- 229910001593 boehmite Inorganic materials 0.000 claims description 19
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 19
- 239000000395 magnesium oxide Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 8
- 241000219782 Sesbania Species 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001404 mediated effect Effects 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 41
- 229910052782 aluminium Inorganic materials 0.000 description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 34
- 239000003054 catalyst Substances 0.000 description 34
- 239000000463 material Substances 0.000 description 30
- 239000004411 aluminium Substances 0.000 description 18
- 239000002131 composite material Substances 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 15
- 229920002223 polystyrene Polymers 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 11
- 229920001223 polyethylene glycol Polymers 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- -1 uses cellulose Chemical compound 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 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 description 5
- 239000004964 aerogel Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000007524 organic acids Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 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 description 1
- 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 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000012687 aluminium precursor Substances 0.000 description 1
- FOJJCOHOLNJIHE-UHFFFAOYSA-N aluminum;azane Chemical compound N.[Al+3] FOJJCOHOLNJIHE-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 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 description 1
- 239000005312 bioglass Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- B01J35/615—
-
- B01J35/63—
-
- B01J35/651—
Abstract
The present invention relates to a kind of alumina support with macroporous structure, contain adjuvant component phosphorus and magnesium in carrier, it is respectively P that the content of adjuvant component phosphorus and magnesium, which accounts for the percentage composition of carrier quality,2O50.1-2.5wt%, MgO 0.1-2.5wt%, pore-size distribution 60-180nm, macropore ratio 2-75%, Kong Rong 0.8-2.0ml/g, specific surface area 250-300m2The characteristics of/g, macroporous aluminium oxide is adjustable with pore size, and macropore ratio can be controlled effectively.Alumina support with macroporous structure can be used for petrochemical industry and field of fine chemical.
Description
Technical field
The present invention relates to a kind of alumina supports and preparation method thereof, and in particular to a kind of aluminium oxide with macroporous structure
Carrier and preparation method.
Background technique
Macroporous oxide is due to using extensively with biggish cellular structure, higher specific surface area, good thermal stability
In fields such as heterogeneous catalyst, catalyst carrier, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance materials.
The carrier of aluminium oxide with macroporous structure is relatively more.CN03126434.4 discloses a kind of macropore alumina supporter,
Containing aluminium oxide, also contain a kind of halogen, on the basis of carrier total amount, which contains the aluminium oxide of 95-99 weight %, with member
Element meter, the halogen of 0.1-5 weight %, acid amount is less than 0.2 mM/gram.The preparation method of macropore alumina supporter includes will
A kind of precursor of aluminium oxide is formed and is roasted, and before molding and roasting, the precursor of aluminium oxide and a kind of expanding agent are mixed
It closes, the expanding agent includes a kind of organic expanding agent and a kind of halide, and maturing temperature is 600-850 DEG C, calcining time 1-10
Hour, the dosage of each component contains final alumina support, on the basis of carrier total amount, the aluminium oxide of 95-99 weight %,
Based on the element, the halogen of 0.1-5 weight %.Organic expanding agent is in starch, synthetic cellulose, polymeric alcohol, surfactant
One or more.Synthetic cellulose is in carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxylated cellulose
It is one or more of.Polymeric alcohol is selected from one or more of polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, and surfactant is selected from rouge
Fat alcohol polyoxyethylene ether, fatty alkanol amide, molecular weight are the acrylic copolymer of 200-10000, in maleic acid copolymer
It is one or more of.CN201110410339.5 provides a kind of high temperature-resistant active aluminum oxide material and preparation method thereof, the oxygen
Change aluminum material to be made by following steps: after macropore boehmite, high viscous boehmite are mixed with additive with water, turn
Speed is to stir evenly under 100-1000r/min, adds the dilute nitric acid reaction that concentration is 30%, until pH is the peptization of 2.0-5.5
When state, it is aged 3-6h in the case where 80 DEG C of -100 DEG C of temperature stir, pore creating material is added at room temperature and stirs evenly, is slurrying, spraying, dry
It is dry, it is roasted at 900 DEG C and aluminium oxide is made.The alumina material has many advantages, such as convenient for batch production and high-ratio surface.?
Specific surface can be kept in 110m for a long time at a temperature of 1000-1100 DEG C2/ g or more；The work of the alumina material preparation method
Skill process is simple, low in cost.Wherein the sky agent of making is selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide or methyl fibre
One of element is tieed up, dosage is the 0-40% of oxide total weight in alumina material." Zhongshan University's journal " (2002,41
(2): 121-122 the method) introduced is as follows: the polystyrene colloidal crystal microballoon that diameter is 600nm is placed on a buchner funnel, so
The ethanol solution of aluminum nitrate and citric acid is added drop-wise to afterwards on glue crystalline substance under suction filtration, is allowed in its fully penetrated gap into microballoon,
Through dry and roasting, polystyrene moulding is removed, macroporous aluminium oxide is obtained." Acta PhySico-Chimica Sinica " (2006,22 (7): 831-
835) method that granular formwork method prepares three-dimensional ordered macroporous alumina is described, this method is as follows: first using emulsion polymerization
Method obtains polystyrene microsphere, and alumina sol is made in aluminum nitrate plus weak aqua ammonia, then stirs the two by a certain percentage mixed
It closes, ultrasonic treatment, then through dry and roasting, obtains macroporous aluminium oxide.CN201010221302.3 (CN102311134A) is open
A kind of spherical integral macroporous alumina and preparation method thereof.Method includes the following steps: by polymer microballoon lotion, oxidation
Aluminum sol and coagulant are mixed in a certain proportion uniformly, which is scattered in oily phase, form w/o type drop, then again
Above-mentioned mixed phase system is heated, makes the alumina sol gelling balling-up in water phase, it is micro- to isolate molding gel from oily phase later
Ball, then the spherical integral macroporous alumina is obtained after aged, dry and roasting in aqueous ammonia medium.The aluminium oxide
Macropore diameter is uniform controllable in the range of less than 1 μm, and the size of spheric granules is controllable, and mechanical strength is higher, forms
Journey is simple and easy to do, convenient for being prepared on a large scale.Polymer microballoon diameter 50-1000nm, the type of polymer microballoon are polystyrene
The esters microballoons such as microballoon, polyaerylic acid N-butyl microballoon, polyacrylate.Coagulant is hexamethylenetetramine, urea.Oil is mutually
Organic hydrocarbon.The invention mainly prepares Integral macroporous alumina, and macropore diameter is uniform controllable.Preparation process uses
Lipid microballoon and coagulant etc..Preparation process is complicated, and reagent raw material used is relatively more.Due to polymer microballoon make
Alumina support internal gutter structure is blind bore, that is to say, that alumina support internal gutter does not have connectivity.
CN201010221297.6 discloses a kind of preparation method of Integral macroporous alumina.Method includes the following steps: aluminium
Source, polyethylene glycol and after being uniformly mixed selected from low-carbon alcohol and water at least one, will low-carbon epoxyalkane be added it is described mixed
It closes in object, obtains Integral macroporous alumina through aging, immersion, drying and roasting.Of the invention preparation method is simple, ring
Border pollution is small, its aperture of gained Integral macroporous alumina is controllable at 0.05-10 μm.Monoblock type macropore oxidation provided by the invention
Object can be applied to the fields such as macromolecular heterogeneous catalysis, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance material.
CN201410347665.X disclose a kind of macropore hold, the preparation method of high-strength alumina, by the way that polyacrylamide, poly- is added
The expanding agents such as vinyl alcohol, alkylcellulose, sesbania powder, starch are obtained containing eurypyloue alumina support, the dosage of expanding agent
The 10-30% of aluminium oxide is accounted for, but not publicly specific pore diameter range.The although available preferable macropore oxidation of hard mould agent method
Alumina supporter, but the dosage of its template causes processing cost to greatly improve more preferably greater than 20%, the decomposition of a large amount of templates
The demand for development of low-carbon environment-friendly is not met.CN201010509425.7 discloses the side of a kind of hydro-thermal and the common reaming of template
Method is acted on, the dosage of template can be reduced with preparing the alumina support containing macroporous structure by the complementary reaming of hydro-thermal
To 3-10%, but hydro-thermal is assisted to cause the raising of energy consumption.CN200310103035.X discloses a kind of macroporous aluminium oxide
Preparation method carries out reaming using polyvinyl alcohol, poly- propyl alcohol, polyethylene glycol soft template, by the way that 1% polyethylene glycol is added,
Kong Rong of the aperture greater than 100nm accounts for the 26.2% of total pore volume.Soft template has the advantages that dosage is low, reaming effect is good, still
The solubility property of the alcohols soft template of higher molecular weight in water is poor, causes it to be used to expand super large porous aluminum oxide and is limited
System.CN200910204238.5 (CN102040235) discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The party
Then method fills certain party legal system the following steps are included: monodispersed polymer microballoon is assembled into glue crystal template into template
Standby alumina sol most obtains macroporous aluminium oxide through dry and roasting afterwards.This method can be good at control Aluminum sol and
The recombination process of Aluminum sol and polymer microballoon does not destroy the network structure of alumina gel as far as possible, makes prepared oxidation
Aluminium not only has the macropore duct of three-dimensional order but also specific surface area with higher.The invention is burnt by the appropriateness to template
The small fenestra tied and formed, makes the macropore in material be connected with the macropore of surrounding by 12 small fenestras.The oxidation of the invention
Aluminium is suitable for use as the adsorption and separation material of mink cell focus catalyst carrier and organic macromolecule.Have in catalyst carrier material application
Conducive to the mass transfer ability of material in the catalyst is improved, be conducive to the activity and selectivity for improving catalyst.
CN201410148773.4 discloses a kind of preparation method of aluminum oxide porous microballoon, comprising the following steps: 1) by surface-active
Agent is dissolved in deionized water, stirring, as water phase；2) chelating agent, alumina precursor and n-octyl alcohol are mixed, is stirred, as
Oily phase；3) Span80 and pore-foaming agent, stirring are added in oily phase；4) clear oil obtained by step 3) is mutually poured into water phase
Continue stirring and emulsifying；5) step 4) gains are filtered by vacuum, it is dry after gained Washing of Filter Cake, obtain aluminum oxide porous microballoon.It should
Microballoon has internal closing macroporous structure, and Microsphere Size is 1 μm -100 μm, and the invention is solidifying using the colloidal sol in pore-foaming agent and lotion
Glue process obtains the metal porous microballoon with internal closing macroporous structure.Porous microsphere is prepared using phase separation principle.It is internal
Closing aperture is 50nm-5 μm.Inside closing aperture is 50nm-5 μm.Aperture is closed inside the aluminum oxide porous microballoon,
That is alumina support internal gutter does not have connectivity.Pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or poly- third
Olefin(e) acid.The invention has used a large amount of surfactant, chelating agent, pore-foaming agent, and it is more to prepare raw material, and synthesis technology is complicated.
The above macroporous aluminium oxide mainly uses cellulose, polymeric alcohol, polystyrene etc. to prepare macropore oxygen as expanding agent
Change aluminium.
Alumina support with macropore and mesoporous i.e. composite pore structural also compares more.CN101200297A discloses whole
The preparation method of figure macroporous aluminium oxide: use reversed concentrated emulsions method big as monomer preparation monoblock type using styrene and divinylbenzene
Hole organic formwork；Al is prepared using aluminium isopropoxide or boehmite as predecessor2O3The hydrosol；By Al2O3The hydrosol is filled into whole
In body formula macropore organic formwork；Filled monolithic devices organic/inorganic composite is removed through drying in 600 DEG C of -900 DEG C of roastings
Template obtains integral macroporous alumina.The advantages of this method is that preparation process is simple and easy, monoblock type macropore oxygen obtained
Change the macropore duct that there is aluminium micron order to interconnect, aperture is 1-50 μm.It is simple that this method prepares Integral macroporous alumina
It is easy, but the volume fraction of water phase accounts for 75%-90% in this method, and correspondingly the volume fraction of organic monomer is relatively low, this
For method while reducing organic monomer consumption, the preparation efficiency of prepared template is relatively low, is unfavorable for subsequent step macropore
It is prepared by the batch of aluminium oxide.A kind of preparation method of the alumina support of composite pore structural of CN201110032234.0, including will
Closing containing calorize selected from least one of aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, aluminium chloride, Aluminum sol and boehmite powder
Object and composite mould plate agent are mixed and are roasted, the composite mould plate agent be mesoporous template and macroporous granules template, it is described mesoporous
Template is selected from polyethylene glycol propylene glycol-polyethylene glycol triblock polymer, polyethylene glycol, lauryl amine, cetyl
At least one of trimethylammonium bromide, lauric acid, stearic acid and fatty alcohol polyoxyethylene ether, the macroporous granules template are selected from
Partial size is residual greater than the polystyrene microsphere of 50nm, poly (methyl methacrylate) micro-sphere, particles of bioglass, pitch particle or heavy oil
Slag；The weight ratio of the mesoporous template, macroporous granules template and aluminum contained compound is 0.1-2:0.1-0.7:1, wherein institute
The weight of aluminum contained compound is stated in terms of aluminium oxide.The invention also discloses have mesopore orbit while preparation by the above method
With the alumina support in macropore duct, intermediary hole accounts for the 40%-90% of total pore volume, and macropore accounts for the 10%-60% of total pore volume.
CN201210328824.2 discloses a kind of method for preparing solid phase of gradient distribution hole gama-alumina.This method is anti-by solid phase
Precursor aluminium carbonate ammonium should be obtained, the gamma oxidation that a kind of high specific surface area, gradient distribution hole and large hole are held is obtained after roasting
Aluminium.The present invention is the most outstanding to be technically characterized in that using raw material solid phase reactive synthesis technique, as obtained by synthesis condition control
The property of gama-alumina.Meanwhile the method for the present invention is simple, and it is easily operated, addition expanding agent is not needed, save the cost is suitble to work
Industryization batch production.The preparation process of alumina support of the present invention the following steps are included: (1) aluminum nitrate, ammonium hydrogen carbonate and table
Face activating agent is fully ground uniformly, and certain time is aged in the closed container of specific temperature and obtains precursor aluminium carbonate ammonium；(2)
It will form after mixing after the drying of precursor aluminium carbonate ammonium obtained by (1) with peptizing agent, can generally be squeezed using banded extruder
Item molding；(3) (2) are obtained that final alumina support is made in molding drying, aerobic roasting.Step lures described in (1)
The polyethylene glycol that agent is liquid form is led, additional amount is equivalent to the 0.1-10.0% of aluminum nitrate weight.Carbonic acid described in step (2)
The drying process of aluminium ammonium is 1-20 hours dry generally at 50-180 DEG C.Roasting process described in step (3) is in 350-900
It is roasted 1-10 hours at DEG C.The invention prepares gama-alumina using the decomposition at a certain temperature of precursor aluminium carbonate ammonium.Aluminium carbonate
Ammonium generates gas, such as NH in decomposable process3And CO2, the generation and evolution of these gases can manufacture some macropores.Simultaneous oxidation
The pattern of aluminium is transformed by the pattern topology of aluminium carbonate ammonium.Slower heating rate is conducive to gas object in roasting process
Matter slowly escapes, and does not easily cause carrier to collapse.Method is simple, does not need to add any physics expanding agent.
CN201310097588.2 discloses a kind of gama-alumina particle and preparation method thereof: 1) aluminum soluble salt being dissolved in by acid
In aqueous solution of the pH value of acidification less than or equal to 3, the amount that the aluminum soluble salt is added makes obtained containing aluminium in aluminum water solution
The molar concentration of ion is 0.01-5mol/L；2) obtained containing alkaline precipitating agent, the alkali is added in aluminum water solution to step 1)
Property precipitating reagent be added amount make reaction after solution ph between 5-12；3) the mixed sediment solution that step 2) obtains is existed
At room temperature stir 0.1-3h after, be put into water-bath or water heating kettle, 50-150 DEG C at a temperature of be aged 6-24h；4) by step
3) solution after being aged is after mixing evenly, dry using spray drying process, and control inlet air temperature is 150-400 when spray drying
DEG C, leaving air temp is 60-110 DEG C, and the thermal efficiency of spray drying is 50% or more；5) oxidation after the drying for obtaining step 4)
Aluminium precursor powder is heated to 250 DEG C -350 DEG C at room temperature with first rate of heat addition, is then heated to second rate of heat addition
400 DEG C -800 DEG C, heat preservation 0.5-20h obtains final product gama-alumina particle；Wherein, first rate of heat addition is less than
Two rates of heat addition, and first rate of heat addition and second rate of heat addition are in the range of 0.1-10 DEG C/min.It is obtained
Gama-alumina is experiments verify that test, specific surface area have high-specific surface area within the scope of 180m2/g-260m2/g.It is made
Gama-alumina particle observed under scanning electron microscope have hollow foam shape pattern, and have micropore-mesopore-macropore it is compound
Aperture structure.In this way, when gama-alumina is as catalyst carrier, hollow foam shape pattern can be effectively in dispersed catalyst
Active component.And hollow foam shape pattern and composite bore diameter structure, be conducive to the mass transfer in catalytic process, to accelerate
Rate of catalysis reaction.The composite bore diameter structure refers to not only include micropore of the aperture less than 2nm, but also including aperture in 2nm-50nm
Between it is mesoporous, further include aperture be greater than 50nm macropore.It further include making to obtained containing being added in aluminum water solution in step 1)
Hole agent, the amount that the pore creating material is added that the molar concentration of pore creating material in rear solution is added to be aluminum ions molar concentration
0.01-5 times.The pore creating material is cetyl trimethylammonium bromide (CTAB), neopelex (SDBS), polyethylene
One or more of alcohol (PVA), polyethylene glycol (PEG) and calgon.CN101863499A
(201010187094.X) provides a kind of preparation method of macroporous-mesoporous alumina.The following steps are included: a. first helps reaction
Agent and aluminium salt are dissolved in organic solvent solution, reaction promoter: two kinds of material mol ratios of aluminium ion are 3-5: 1, then by template
Above-mentioned solution is added and dissolves, aluminium ion and template molar ratio are 1: 0.015-0.025, and the pH value control of final solution exists
3.5-6.0；B. the solution by a step preparation carries out aging process, so that it is gradually removed organic solvent and moisture in system and obtains greatly
Hole-meso-porous alumina presoma；C. macroporous-mesoporous alumina powder is obtained through 400-800 DEG C of calcination process.Present invention process letter
Single, duct rule, pore-size distribution is concentrated and can realize controllable adjustment according to concrete application situation, thus more in petrochemical industry
Mutually catalysis, adsorbing separation and have important application value as catalyst carrier, energy and material etc..It makes full use of anti-
The space frame effect and coordination and intermediary's organic polymer, reaction promoter for answering auxiliary agent and template are to inorganic ions
Complexing, so that a step prepares the adjustable macroporous-mesoporous alumina material in aperture.Prepared foramen magnum-mesoporous oxidation
The specific surface area of aluminum material is up to 250-320m2/ g, duct rule, pore-size distribution in mesoporous 5-40nm, macropore 50-150nm, and
Adjusting can be realized according to the actual situation.Reaction promoter is organic acid, and aluminium salt is inorganic aluminate.Template is triblock copolymer.
Organic solvent is anhydrous alcohols, ethers or ketones solvent.Organic acid is citric acid or lauric acid.Triblock copolymer is
P123 or F127.Tie-Zhen Ren etc. (Langmuir, 2004,20:1531-1534) uses nonionic surfactant
56 aluminium secondary butylate of Brij uses hydro-thermal method and Microwave-assisted synthesis macroporous-mesoporous alumina in acid condition, synthesis it is porous
0.8-2 μm of alumina powder macropore diameter, mesoporous pore size 5-8nm, 0.4-1.4 μm of hole wall of aluminium oxide.Its deficiency is aluminium-alcohol salt
Expensive, the macroporous-mesoporous alumina Kong Rong little of synthesis, duct is irregular, pore-size distribution is excessive and cannot achieve pore structure
Effective adjusting thus have significant limitation in using effect and range.Jean-Philippe Dacquin etc.
It using P123 is template in mixed solution that (J.Am.Chem.Soc., 2009,131:12896-12897), which uses sol-gel method,
It is middle to be introduced into the polystyrene droplet with single dispersed phase to realize the formation of macropore in macroporous-mesoporous alumina.Deficiency
Place is that macropore diameter size (300nm or 400nm) is determined by the secondary size for introducing polystyrene drop completely, i.e. macropore diameter
Size depends on polystyrene droplet size.Organic molecule in the change of the part to solution itself component and system can not be passed through
It interacts to realize the adjustment in aperture.Huining Li et al. (Inorganic Chemistry, 2009,48:4421) is equally adopted
The polymethyl methacrylate with single dispersed phase is introduced in mixed solution with sol-gel method by template of F127
(PMMA) droplet realizes the formation of macropore in macroporous-mesoporous alumina, shortcoming be macropore diameter size also completely by
Secondary introducing polymethyl methacrylate droplet size determines, can not be changed by the part to solution system itself component come real
The adjustment in existing aperture also cannot achieve the controllable of foramen magnum-mesoporous aperture to realize the formation of foramen magnum-mesoporous composite pore structural
Adjust, in use, in particular for complicated ingredient bulky molecular catalysis during by significant limitation.
The above composite holes alumina support generally uses organic polymer such as polyvinyl alcohol, polymethylacrylic acid etc. as mould
Plate agent either expanding agent.So that the preparation of composite holes and macroporous aluminium oxide material there are the monomer of template have certain toxicity,
The problems such as template consumption is larger, preparation cost is higher, preparation process is cumbersome.Meanwhile there is also the discharges in roasting process
The problem of object environmental pollution.Also there is the patent that saccharide compound is added in polymer microballoon lotion.
CN201310142454.8 discloses a kind of preparation method of alumina hollow ball, and it is water-soluble to prepare chitosan-acetic acid-
Liquid；By polystyrene spheres: chitosan-acetic acid-aqueous solution be 5:1-10:1 mass ratio, press polystyrene spheres: alpha-alumina
Body is that the mass ratio of 1:5-1:15 takes each raw material；Polystyrene spheres and chitosan-acetic acid-aqueous solution are mixed, polyphenyl is made
Ethylene ball surface uniformly coats one layer of chitosan-acetic acid-aqueous solution；It is coated with chitosan-acetic acid-aqueous solution polyphenyl second again
In alkene ball and alpha-alumina powder investment ball-milling device, with the revolving speed rotation cladding 2-24h of 5-30r/s, obtained core-shell structure copolymer ball；It will
After the calcining of core-shell structure copolymer ball warp, the alumina hollow ball that diameter is 0.2-2mm, wall thickness is 20-100 μm is obtained.
CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The three-dimensional ordered macroporous oxidation
Aluminium, diameter macropores 50-1000nm, grain diameter 1-50mm, mechanical strength 80-280g/mm.This method includes following step
It is rapid: saccharide compound and the concentrated sulfuric acid will to be added into monodisperse polymer micro-sphere lotion, obtain polymer-modified microballoon glue crystalline substance mould
Plate is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous alumina.The polymer microballoon
Diameter is 50-1000nm, can be used polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyacrylic acid N-butyl microballoon and
One of different monooctyl ester microballoon of polyacrylic acid is a variety of, preferably polystyrene microsphere.The monodisperse refers to polymer microballoon
The standard deviation of diameter is not more than 10%.The carbohydrate organic matter be one of Soluble Monosaccharide and polysaccharide or a variety of, preferably
For one of sucrose, glucose, chitosan or a variety of.This method can increase substantially the adhesion amount of aluminium oxide precursor, increase
The strong mechanical strength of material, it is subtle powder that when removing template is removed in high-temperature roasting, large pore material is not easily broken, can still be protected
Hold higher integrity degree.Chitosan is in ceramic coating adsorbent material field using more." mesoporous chitosan-aluminium hydroxide is compound
Material Study on adsorption properties " (author: Peng Shaohua] University Of Suzhou, " Suzhou Institute of Science and Technology journal: natural science edition " 2013 30
Rolled up for 4 phases): with chitosan and AlCl3For raw material, it is prepared for chitosan and α-Al (OH)3Composite material.With X-ray powder diffraction,
Transmission electron microscope, infrared, thermogravimetric and specific surface instrument characterization has been carried out to it the result shows that: α-Al (OH)3It is in chitosan complexes
Now typical mesoporous characteristic, BET specific surface area 55.4m2·g-1, BJH average pore size is 3.3nm；Specifically the preparation method comprises the following steps: claiming
It takes 2.0g Aluminium chloride hexahydrate to be dissolved in the hydrochloric acid that 5.0mL pH value is 1,2.0g chitosan, then plus 10.0mL distilled water is added
Stirring, and the pH value of solution is adjusted to 1 with dilute hydrochloric acid.Still aging 30min (solution becomes paste), the NaOH for being 14 with pH value
Solution adjusts the pH value of solution to 8, has white flock precipitate generation, filters, wash away remaining NaOH with distilled water, be put into baking
Case obtains product after 120 DEG C of heat preservation 5h.Step as above, prepare chitosan respectively and aluminium chloride mass ratio be respectively 1:2,1:3,
The product of 2:1,3:1.
" preparation and characterization of chitosan/oxidized aluminium composite aerogel " (Chang Xinhong；The chemicalization engineering of Luoyang Normal College
Institute, " Luoyang Normal College's journal ", 11 phases of volume 31 in 2012): with chitosan and inorganic aluminate AlCl3.6H2O is raw material, is passed through
Sol-gel process uses CO respectively2Supercritical drying means and freeze-drying means are prepared for novel chitosan/oxidized aluminium
Composite aerogel.The result shows that the content of chitosan influences the properties such as specific surface area and the pore volume of composite aerogel, with shell
The increase of glycan content, the specific surface area for mixing aeroge are gradually reduced.Ratio table of the different drying means to composite aerogel
The properties such as area also have apparent influence.Composite aerogel contains micropore and mesoporous.CN201110022814.1 one kind has super
The ordered mesoporous metal oxide material of large aperture, it is characterised in that utilize the amphipathic block with ultrahigh molecular weight hydrophobic section
Copolymer is as structure directing agent, according to the principle of ligand assisted self assembling, before making mesoporous material during solvent volatilization
It drives and is acted between body and structure directing agent, and microphase-separated is differently formed according to hydrophilic and hydrophobic, ultimately form orderly to be situated between and see knot
Structure；After removing structure directing agent again, the ordered mesoporous metal oxide material with ultra-large aperture is formed；Wherein, block copolymerization
The molecular weight of the hydrophobic block of object is greater than 10000g/mol；The ordered mesoporous metal oxide material mesoporous pore size is in 10-50nm
Between, mesoporous wall thickness of material is between 4-20nm.The hydrophilic block of the block copolymer is polyoxyethylene blocks；Institute
The hydrophobic block for stating block copolymer is polystyrene or derivatives thereof, polyacrylate or derivatives thereof, polymethylacrylic acid
The copolymer of ester or derivatives thereof, one kind of polylactic acid pole or derivative or two or more polymer described above.The invention system
Standby is meso-porous alumina, similar also CN101153051A, CN1631796A, CN101134567A, CN101823706A,
CN101863499A.CN201310258011.5 is related to a kind of tooth spherical alumina support, tooth ball-aluminium oxide hydrotreating is urged
Agent and preparation method thereof, including following components: peptizing agent, 0.5-4 parts by weight；Lubricant, 0.2-2 parts by weight；Dispersing agent,
0.2-3 parts by weight；Expanding agent, 0.3-4 parts by weight；Aluminium hydroxide, 100 parts by weight.Expanding agent is polyvinyl alcohol, polyacrylic acid
One of sodium, starch derivatives or carbon black or mixture.The invention, which is added to anionic surfactant, reduces various help
Specific surface area increases 246m while agent ingredient additive amount2/ g, expanding agent Sodium Polyacrylate.The oxidation of tooth spherical shape described in the invention
Alumina supporter, since the wherein groups such as various auxiliary agents such as peptizing agent, expanding agent, dispersing agent, anionic surfactant are greatly lowered
The content divided, has not only saved cost, has also had many advantages, such as large specific surface area, high mechanical strength.The invention has used peptizing agent,
Lubricant, dispersing agent, the reagents such as expanding agent, obtained alumina support are unimodal pore size distributions.CN201110116418.5 is mentioned
It has supplied a kind of mesoporous sphere aluminium oxide and has been oriented to the method for preparing the mesoporous sphere aluminium oxide using template.Using oil column at
The template with guide function is added in type method during preparing Aluminum sol into Aluminum sol, and Aluminum sol is in molding and aging
In the process, since the presence of the template with guide function makes to produce a large amount of meso-hole structure in alumina balls.Template
For organic monomer or linear polymer, organic monomer is one of acrylic acid, ammonium acrylate, acrylamide, allyl alcohol.Jie
Hole ball-aluminium oxide specific surface is 150-300m2/ g, particle diameter 0.1-5mm, pore volume 0.7-1.5ml/g, bore dia are
The hole of 2-40nm is greater than 97%, and heap density is 0.30-0.80g/cm3, crushing strength is 70-250N/.The invention utilizes template
The mesoporous sphere alumina pore diameter of agent preparation compares concentration, this kind of mesoporous sphere aluminium oxide can be used for petrochemical industry and fining
Work is catalyst or catalyst carrier.
Macroporous aluminium oxide and compound porous aluminum oxide have different journeys to activity, selectivity and the stability aspect of catalyst
The improvement result of degree.The solubility of polyvinyl alcohol template in water is influenced by the degree of polymerization, it is caused to be used for super big hole oxygen
Change and is also subject to certain restrictions in the preparation of aluminium.
Summary of the invention
The present invention provides a kind of alumina support with macroporous structure, and using chitosan as expanding agent, synthesis is provided
There is the alumina support of macroporous structure.Macroporous aluminium oxide is adjustable with pore size, the spy that macropore ratio can be controlled effectively
Point.Alumina support with macroporous structure can be used for petrochemical industry and field of fine chemical.
The present invention provides a kind of alumina support with macroporous structure, contains adjuvant component phosphorus and magnesium, auxiliary agent in carrier
The percentage composition that the content of component phosphorus and magnesium accounts for carrier quality is respectively P2O50.1-2.5wt%, MgO 0.1-2.5wt%, hole
Diameter is distributed 60-180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, Kong Rong 0.8-2.0ml/g, preferably
0.8-1.3ml/g or preferred 1.6-2.0ml/g, specific surface area 250-300m2/g.Carrier uses chitosan as expanding agent.
The present invention has the alumina support of macroporous structure, and aperture can pass through the additional amount and reaming of variation expanding agent
The molecular size range of agent is adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-160nm,
The ranges such as 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, the ranges such as 35-50%, 55-75%.
The present invention also provides a kind of preparation methods of alumina support with macroporous structure, firstly, being acidified with acid solution
Then boehmite and sesbania powder are added in kneader and are uniformly mixed by chitosan, add the mixed of phosphoric acid and magnesium nitrate
Solution is closed, finally the acid solution of chitosan-containing is added in boehmite powder and is mediated uniformly, the acid solution containing expanding agent
Additional amount be boehmite 0.1-8wt%, preferably 0.2-5.0wt% obtained by extrusion-molding-drying-roasting
Alumina support with macroporous structure.
The process of the acid solution acidified chitosan is as follows: first by chitosan expanding agent be added to 30-95 DEG C go from
In sub- water, acid is added dropwise later, until chitosan dissolution is completely, obtains the acid solution containing expanding agent.The acid can be inorganic acid
Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The additional amount of acid is advisable with that can be completely dissolved chitosan.It can also
To select water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc..Chitosan acid solution is best
With ultrasonic oscillation or magnetic agitation.Ultrasonic oscillation 10min or more, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent
Wave concussion or magnetic agitation, expanding agent good dispersion, alumina support is more prone to produce macropore, and pore-size distribution more collects
In, pore-size distribution is in 70-180nm.
The additional amount of the sesbania powder is the 0.1-7wt% of boehmite.
It mediates or extrusion technique is that the configured acid solution containing expanding agent is added in sesbania powder and boehmite
Be uniformly mixed, later extrusion, molding, by 100-160 DEG C drying 3-9 hours, 650-800 DEG C roasting 4-8 hours, finally obtain
Alumina support with macroporous structure.
The present invention uses chitosan for expanding agent, and the alumina support of preparation contains macroporous structure, while also containing mesoporous
Structure, macropore range are a kind of containing Jie-macropore carrying alumina in 2-50nm, mesoporous ratio 15-75%, preferably 15-50%
Body.And aperture is not uniform aperture structure.
The alumina support with macroporous structure obtained using preparation method of the present invention can also utilize phosphorus and magnesium
Carrier surface is modified, the concentration of phosphorus and magnesium is unsuitable excessively high, and preferably configuration concentration is lower than phosphorus when preparing complex carrier
Acid and magnesium nitrate aqueous solution spray carrier surface, preferably carry out carrier surface modification as follows: configuration phosphoric acid and nitre
The aqueous solution spray of sour magnesium has the alumina support of macroporous structure, obtains used additives phosphorus through drying, roasting and magnesium carries out surface
Modified alumina support controls phosphorus pentoxide and content of magnesia in the alumina support with macroporous structure and exists respectively
In the range of 0.1-2.5wt% and 0.1-2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is made to be inside five
Aoxidize 1.05-1.6 times of two phosphorus and content of magnesia.
Compared with prior art, the invention has the following advantages that
1, for the present invention using chitosan as expanding agent, expanding agent chitosan is cheap, and environment-protecting and non-poisonous, is suitble to work
Industry metaplasia produces.The obtained alumina support with macroporous structure, pore size is adjustable, and macropore ratio can be controlled effectively.
And carrier also contains mesoporous, is a kind of Jie-macropore alumina supporter.
2, the present invention can also introduce phosphorus and magnesium in alumina support, the obtained carrying alumina with macroporous structure
Body, the carrier are prepared into Hydrobon catalyst, such as the catalyst such as cobalt molybdenum or nickel molybdenum, are able to suppress alkene saturated activity, urge
Agent desulfurization degree is high, and alkene saturation factor (HYD) is low, has good hydrodesulfurization selectivity.
3, the alumina support with macroporous structure that the present invention obtains, using phosphorus and magnesium to the oxidation with macroporous structure
Alumina supporter surface is modified, and the content of carrier surface phosphorus pentoxide and magnesia is made to be internal phosphorus pentoxide and oxidation
1.05-1.6 times of content of magnesium.Carrier surface is modified by the way of spray, is capable of the portion of effective peptization carrier surface
Divide micropore, advantageously reduce the micropore ratio of carrier surface in this way, improve carrier surface Jie-macropore ratio, promotes carrier surface
More active sites load centres are produced, catalyst desulfurizing activity is effectively improved.Dipping should not be used to the improvement of carrier surface
Method, impregnated carrier surface can make large quantity of moisture enter carrier, and intensity is deteriorated, and are not achieved and improve carrier surface Jie-macropore ratio
Purpose.
4, the aluminium oxide of the present invention with macroporous structure can be used for pyrolysis gasoline hydrogenation desulfurization, remove as carrier
Alkynes；It can be used for gasoline hydrodesulfurizationmethod modification, demercaptaning for gasoline, petroleum naphtha hydrogenation dearsenification desulfurization, oligomerisation, monoolefine, diene
Hydrocarbon, alkynes and benzene hydrogenation, the fields such as adding hydrogen into resin.Activity, selection with Jie-macroporous structure alumina support to catalyst
Property and stability etc. have different degrees of improvement result.
Detailed description of the invention
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
Embodiment 1
8.0g water soluble chitosan expanding agent is added in 50 DEG C of deionized water first, acetic acid is added dropwise later, until
Chitosan dissolution completely, obtains the acid solution containing expanding agent.Phosphatase 11 .46g, magnesium nitrate 7.35g are weighed respectively, by phosphoric acid and nitre
Sour magnesium, which is dissolved completely in 70g distilled water, is made into phosphorous, magnesium aqueous solution.Weigh 350g boehmite powder and the field 20.0g
Cyanines powder is added in kneader, and is uniformly mixed, and the mixed solution of phosphoric acid and magnesium nitrate is added, finally by the acid of chitosan-containing
Solution, which is added in boehmite powder, to be mediated uniformly, is clover shape by kneading-extruded moulding.At 120 DEG C dry 8
Hour, 700 DEG C roast 4 hours, obtain phosphorous and magnesium alumina support 1.Phosphorus pentoxide 0.5wt%, magnesia in carrier 1
0.8wt%.Alumina support specific surface area and pore-size distribution with macroporous structure are shown in Table 1.
Cobalt nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body 1,5 hours dry at 130 DEG C, 650 DEG C roast 7 hours, obtain Hydrobon catalyst 1.Catalyst 1 mainly forms: oxygen
Change cobalt 3.5wt%, molybdenum oxide 9.5wt%, changes alumina supporter 87.0wt%.
Embodiment 2
8.0g water soluble chitosan expanding agent is added in 50 DEG C of deionized water, acetic acid is added dropwise later, until shell is poly-
Sugar dissolution completely, obtains the acid solution containing expanding agent.Phosphatase 11 .09g, magnesium nitrate 9.12g are weighed respectively, by phosphoric acid and magnesium nitrate
It is dissolved completely in 70g distilled water and is made into phosphorous, magnesium aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania powder
It is added in kneader, and is uniformly mixed, add the mixed solution of phosphoric acid and magnesium nitrate, finally by the acid solution of chitosan-containing
It is added in boehmite powder and mediates uniformly, be clover shape by kneading-extruded moulding.It is small in 120 DEG C of dryings 8
When, 700 DEG C roast 4 hours, obtain phosphorous and magnesium alumina support 1.It recycles phosphorus and magnesium to be modified carrier surface, matches
Alumina support 1 of the aqueous solution spray with macroporous structure of phosphoric acid and magnesium nitrate is set, it is 8 hours, 700 DEG C dry through 120 DEG C
Roasting obtains used additives phosphorus for 4 hours and magnesium carries out the modified alumina support 2 in surface, carrier surface phosphorus pentoxide and magnesia
Content be 1.2 times of internal phosphorus pentoxide and content of magnesia.Alumina support specific surface area with macroporous structure with
Pore-size distribution is shown in Table 1.
Cobalt nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body 2,6 hours dry at 110 DEG C, 600 DEG C roast 5 hours, obtain Hydrobon catalyst 2.Catalyst 2 mainly forms: oxygen
Change cobalt 6.2wt%, molybdenum oxide 11.1wt%, alumina support 82.7wt%.
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.The difference is that water soluble chitosan expanding agent is changed to
Water-insoluble chitosan expanding agent, chitosan formic acid liquid was with magnetic stirrer 30 minutes.Obtain the oxygen with macroporous structure
Change alumina supporter 3.The percentage composition that the content of adjuvant component phosphorus and magnesium accounts for carrier quality in carrier is respectively P2O51.8wt%, MgO
2.0wt%.Its specific surface area and pore-size distribution are shown in Table 1.
Cobalt nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body 3,6 hours dry at 120 DEG C, 650 DEG C roast 5 hours, obtain Hydrobon catalyst 3.Catalyst 3 mainly forms: oxygen
Change cobalt 5.1wt%, molybdenum oxide 7.6wt%, alumina support 87.3wt%.
Embodiment 4
The preparation method of carrier is carried out according to embodiment 1.The difference is that water soluble chitosan expanding agent is changed to
Water-insoluble chitosan expanding agent, chitosan acetic acid solution was with ultrasonic oscillation 15 minutes.Obtain the aluminium oxide with macroporous structure
Carrier.The percentage composition that the content of adjuvant component phosphorus and magnesium accounts for carrier quality in carrier is respectively P2O50.8wt%, MgO
1.0wt%.It recycles phosphorus and magnesium to be modified carrier surface, obtains carrier 4,4 surface phosphorus pentoxide of carrier and magnesia
Content be 1.5 times of internal phosphorus pentoxide and content of magnesia.4 specific surface area of alumina support with macroporous structure with
Pore-size distribution is shown in Table 1.
Cobalt nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body 4,6 hours dry at 120 DEG C, 580 DEG C roast 6 hours, obtain Hydrobon catalyst 4.Catalyst 4 mainly forms: oxygen
Change cobalt 2.2wt%, molybdenum oxide 10.3wt%, alumina support 87.5wt%.
Catalyst 1-4 is respectively charged into 10ml fixed bed reactors, evaluation catalyst reaction performance is carried out.Use sulfurized oil
Presulfurization is carried out to catalyst, sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, concentration 1.0wt%；Sulfide stress is
2.8MPa, hydrogen to oil volume ratio 300, sulfurized oil volume space velocity are 3.0h-1, vulcanization program is respectively in 220 DEG C, 280 DEG C of vulcanizations
Handle 6h.After vulcanizing treatment, be switched to full fraction FCC gasoline replacement Treatment 8h, to pre-vulcanization process after, be adjusted to
Reaction process condition is reacted into catalytically cracked gasoline.Reaction process condition are as follows: 230 DEG C of temperature of reactor, reaction pressure
1.4MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio 210.Sampling analysis, catalyst and contrast medium reactor product after reaction about 55h
Property is shown in Table 2.
The alumina support specific surface area and pore-size distribution of 1 macropore of table
2 catalyst reaction product property of table
Hydrobon catalyst 1-4 loss of octane number is low, and desulfurization degree is high, and activity is good, has good hydrodesulfurization selection
Property.Reaction operation 500h, 4 product desulfurization degree of Hydrobon catalyst are 82.7%, alkene drop amount 2.3%, and loss of octane number is
0.3 unit, alkene saturation factor (HYD) are 9%, and the complex carrier surface of catalyst produces in more active sites loads
The heart, effectively improves catalyst desulfurizing activity, and catalyst reaction performance is stablized.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (7)
1. a kind of alumina support with macroporous structure, it is characterised in that:
Contain adjuvant component phosphorus and magnesium in carrier, the percentage composition that the content of adjuvant component phosphorus and magnesium accounts for carrier quality is respectively
P2O50.1-2.5wt%, MgO 0.1-2.5wt%, pore-size distribution 60-180nm, macropore ratio 2-75%, Kong Rong 0.8-
2.0ml/g, specific surface area 250-300m2/ g, carrier use chitosan as expanding agent；
The alumina support with macroporous structure, macropore range is in 5-50nm, mesoporous ratio 15-50%；
The preparation method of the alumina support with macroporous structure, includes the following steps:
Firstly, then boehmite and sesbania powder are added in kneader and are uniformly mixed with acid solution acidified chitosan, then
The mixed solution of phosphoric acid and magnesium nitrate is added, finally the acid solution of chitosan-containing is added in boehmite powder and is mediated
Even, the additional amount of the acid solution containing expanding agent is that the 0.1-8wt% of boehmite is obtained by extrusion-molding-drying-roasting
To the alumina support with macroporous structure；Drying-the roasting, refer to by 100-160 DEG C drying 3-9 hours, 650-
800 DEG C roasting 4-8 hours；
To the obtained alumina support with macroporous structure, carrier surface is modified using phosphorus and magnesium: configuration phosphoric acid
There is the alumina support of macroporous structure with the aqueous solution spray of magnesium nitrate, obtain used additives phosphorus through drying, roasting and magnesium carries out
The modified alumina support in surface controls phosphorus pentoxide and content of magnesia difference in the alumina support with macroporous structure
In the range of 0.1-2.5wt% and 0.1-2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is made to be internal
1.05-1.6 times of phosphorus pentoxide and content of magnesia.
2. a kind of alumina support with macroporous structure according to claim 1, it is characterised in that: described having is big
The alumina support of pore structure, pore-size distribution is in 65-150nm, macropore ratio 5-65%, Kong Rong 0.8-1.3ml/g.
3. a kind of alumina support with macroporous structure according to claim 1, it is characterised in that: described having is big
The alumina support of pore structure, for pore-size distribution in 60-90nm, macropore ratio is 35-50%.
4. a kind of alumina support with macroporous structure according to claim 1, it is characterised in that: described having is big
The alumina support of pore structure, for pore-size distribution in 100-160nm, macropore ratio is 55-75%.
5. a kind of preparation method of any alumina support with macroporous structure of claim 1-4, it is characterised in that:
Include the following steps:
Firstly, then boehmite and sesbania powder are added in kneader and are uniformly mixed with acid solution acidified chitosan, then
The mixed solution of phosphoric acid and magnesium nitrate is added, finally the acid solution of chitosan-containing is added in boehmite powder and is mediated
Even, the additional amount of the acid solution containing expanding agent is that the 0.1-8wt% of boehmite is obtained by extrusion-molding-drying-roasting
To the alumina support with macroporous structure；Drying-the roasting, refer to by 100-160 DEG C drying 3-9 hours, 650-
800 DEG C roasting 4-8 hours；
To the obtained alumina support with macroporous structure, carrier surface is modified using phosphorus and magnesium: configuration phosphoric acid
There is the alumina support of macroporous structure with the aqueous solution spray of magnesium nitrate, obtain used additives phosphorus through drying, roasting and magnesium carries out
The modified alumina support in surface controls phosphorus pentoxide and content of magnesia difference in the alumina support with macroporous structure
In the range of 0.1-2.5wt% and 0.1-2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is made to be internal
1.05-1.6 times of phosphorus pentoxide and content of magnesia.
6. a kind of preparation method of alumina support with macroporous structure according to claim 5, it is characterised in that: institute
State is with acid solution acidified chitosan: chitosan expanding agent being added in 30-95 DEG C of deionized water first, is added dropwise later
Acid obtains the acid solution containing expanding agent until chitosan dissolution is completely.
7. a kind of preparation method of alumina support with macroporous structure according to claim 5, it is characterised in that: institute
Stating acid solution is one or more of acetic acid, formic acid, malic acid or lactic acid, chitosan acid solution ultrasonic oscillation or magnetic
Power stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710409026.5A CN106994361B (en) | 2017-06-02 | 2017-06-02 | A kind of alumina support and preparation method with macroporous structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710409026.5A CN106994361B (en) | 2017-06-02 | 2017-06-02 | A kind of alumina support and preparation method with macroporous structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106994361A CN106994361A (en) | 2017-08-01 |
| CN106994361B true CN106994361B (en) | 2019-07-12 |
Family
ID=59436361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710409026.5A Active CN106994361B (en) | 2017-06-02 | 2017-06-02 | A kind of alumina support and preparation method with macroporous structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106994361B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993841A (en) * | 2018-09-01 | 2018-12-14 | 张家港市东威新材料技术开发有限公司 | A kind of preparation method of wear-resisting type alumina composite material |
| CN110734097B (en) * | 2019-10-23 | 2022-03-04 | 中国人民解放军国防科技大学 | ZIF 67-containing derived composite carbon material lithium-sulfur battery positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and lithium-sulfur battery |
| CN111484049B (en) * | 2020-04-17 | 2021-06-18 | 中国科学院过程工程研究所 | Alumina and preparation method and application thereof |
| CN111380994B (en) * | 2020-05-15 | 2023-02-28 | 淄博山分分析仪器有限公司 | Preparation method of chromatographic rod for rod-shaped thin-layer chromatography |
| CN112619637A (en) * | 2020-12-29 | 2021-04-09 | 中国华电科工集团有限公司 | Preparation method of heterogeneous solid catalyst for preparing ammonia by urea hydrolysis |
| CN113097228B (en) * | 2021-03-24 | 2023-10-03 | 深圳市华星光电半导体显示技术有限公司 | Shading substrate, preparation method thereof and array substrate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066530A (en) * | 2006-05-22 | 2007-11-07 | 林方 | Hydrodemetalizing catalyst and its prepn |
| CN101172258A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Modified alumina carrier with composite pore structure and preparation method thereof |
| CN101121899B (en) * | 2006-08-11 | 2010-05-12 | 中国石油化工股份有限公司 | Selectivity hydrogenation method for whole fraction crack petroleum |
| CN103706408B (en) * | 2013-12-18 | 2016-08-17 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method thereof |
-
2017
- 2017-06-02 CN CN201710409026.5A patent/CN106994361B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106994361A (en) | 2017-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106994361B (en) | A kind of alumina support and preparation method with macroporous structure | |
| CN107081155B (en) | A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization | |
| CN107096552B (en) | A kind of catalyst and preparation method for FCC gasoline removal of mercaptans | |
| CN107159283B (en) | A kind of method of cracking c5-C9 fraction selective hydrogenation | |
| CN107185567B (en) | A kind of nickel system selective hydrocatalyst and preparation method thereof | |
| CN107177371B (en) | A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline | |
| CN107159279B (en) | A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof | |
| CN101683983B (en) | Method for preparing hollow mesoporous lamella spherical silica material | |
| CN103936027B (en) | Controlled SAPO-34 zeolitic material of colored shape of nanometer sheet assembling and preparation method thereof | |
| JPS5973432A (en) | Manufacture of alumina bead by dripping coagulation | |
| CN108483473A (en) | Mesopore-macropore composite pore structural silicon-aluminum oxide material and preparation method thereof | |
| CN107057757B (en) | A kind of method of one-stage selective hydrogenation of gasoline splitting | |
| CN109894122A (en) | A kind of FCC gasoline Hydrobon catalyst and preparation method thereof | |
| CN102020283A (en) | Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter | |
| CN107177370B (en) | A method of being used for FCC gasoline removal of mercaptans | |
| CN108236968A (en) | A kind of alumina support of containing mesopore/macropore and preparation method thereof | |
| CN103449406B (en) | A kind of Powdered charcoal-aero gel and its preparation method and application | |
| CN104891539A (en) | Chambering method for spherical aluminum oxide particles | |
| CN107189812B (en) | A method of cracking C6-C8 fraction selective hydrogenation | |
| CN110156038A (en) | A kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve and its preparation method and application | |
| CN107913691A (en) | Alumina support containing macropore and preparation method thereof | |
| CN108452839B (en) | Mesoporous-microporous composite molecular sieve, catalyst, preparation method and application thereof | |
| CN109304226A (en) | A kind of hydrocracking catalyst and its preparation method and application of fecund heavy naphtha and boat coal | |
| CN107189811B (en) | A kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method | |
| CN110386613A (en) | A kind of preparation method for the mesoporous alumina hydrate microspherical of graduation that crystal form is controllable |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |