CN110935430A - 钛改性大孔氧化铝及其制备方法 - Google Patents
钛改性大孔氧化铝及其制备方法 Download PDFInfo
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- CN110935430A CN110935430A CN201811113822.5A CN201811113822A CN110935430A CN 110935430 A CN110935430 A CN 110935430A CN 201811113822 A CN201811113822 A CN 201811113822A CN 110935430 A CN110935430 A CN 110935430A
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- Prior art keywords
- titanium
- alumina
- macroporous alumina
- aluminum
- soaking
- Prior art date
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 58
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 31
- 239000010936 titanium Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 14
- 239000011148 porous material Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 229910001593 boehmite Inorganic materials 0.000 claims description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- -1 amide compound Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 claims description 4
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 18
- 239000002131 composite material Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000013507 mapping Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- YQXQWFASZYSARF-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC YQXQWFASZYSARF-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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Abstract
本发明公开了一种钛改性大孔氧化铝，该氧化铝具有如下性质：大孔氧化铝为γ晶态，总孔隙率60%‑85%，所述的大孔孔径为100‑1000nm，大孔占总孔隙率的比例为40%‑90%；大孔分布均匀且三维贯通；大孔壁厚与孔径尺寸比值为0.5‑4.5；侧压破碎强度为8‑25N/mm。本发明的钛改性大孔氧化铝，钛元素在氧化铝体相均匀分散及掺杂，钛含量以氧化钛计为0.5wt%‑45wt%。本发明的钛改性大孔氧化铝的BET比表面积为200‑450m2/g，孔容为0.50‑1.50cm3/g。本发明的大孔氧化铝，大孔具有三维贯通性，材料机械强度高，能够满足现有多相催化反应的强度要求，可作为催化剂的良好载体使用。
Description
技术领域
本发明涉及一种钛改性大孔氧化铝及其制备方法，属于无机材料制备领域。
背景技术
随着原油日趋重质化、劣质化以及环保法规的严格，汽油和柴油的加氢工艺逐渐向加工高硫油和生产超低硫的清洁环保石油燃料方向转移。催化剂的研发是加氢工艺的核心，加氢催化剂最常用的载体是γ-氧化铝。为开发新型高效的加氢催化剂，单纯的氧化铝载体难以很好地满足加氢技术的需求，因此，通过引入特定元素制备复合氧化铝载体很有必要。氧化钛具有良好的酸性和抗积炭、抗中毒能力，但由于比表面积及孔容较小，自身不适合用于催化载体材料。如将其作为改性组分引入到氧化铝上形成复合载体，复合物则兼具氧化铝的高比表面积、高孔容及氧化钛的良好的酸性和抗积炭、抗中毒能力等优点。
“钛改性纳米自组装大孔氧化铝载体的制备及表征”（应用化工，2016，45（9）：1788-1802）采用四氯化钛为原料制备了钛改性纳米自组装大孔氧化铝载体，复合载体具有最适宜加氢催化的孔道和表面酸性。但所采用的超增溶自组装法与硝酸盐乳化炸药制备体系非常类似，在高温高压的反应下爆炸隐患较大。同时，所用四氯化钛溶液易水解生成二氧化钛大颗粒，致使钛元素在材料中分布不均匀。
“钛铝复合氧化物载体的制备及其性能研究”（无机盐工业，2018，50（3）：74-76）采用共沉淀法制备了钛铝复合氧化物，所得产物没有三维大孔结构。
CN99113284.X制备了含钛氢氧化铝，但由于钛盐溶液中含有氯离子及硫酸根等离子会腐蚀设备，焙烧时产生的排放物环境污染严重，所得产物不具备三维大孔结构。
发明内容
针对现有技术的不足，本发明提供了一种钛改性大孔氧化铝及其制备方法。该大孔氧化铝的大孔三维贯通，材料机械强度高，能够满足现有多相催化反应的强度要求，可作为催化剂的良好载体使用。
本发明的钛改性大孔氧化铝，具有如下性质：大孔氧化铝为γ晶态，总孔隙率60%-85%，所述的大孔孔径为100-1000nm，大孔占总孔隙率的比例为40%-90%，优选为50%-70%；大孔分布均匀且三维贯通；大孔壁厚与孔径尺寸比值为0.5-4.5，优选为1-4；侧压破碎强度为8-30N/mm，优选为10-25N/mm。本发明的钛改性大孔氧化铝，钛以二氧化钛的形式在氧化铝体相均匀分散及掺杂，钛元素团簇尺寸为0.5nm-2.5nm。钛含量以二氧化钛计为0.5wt%-45wt%，优选为1wt%-35wt%。本发明的钛改性大孔氧化铝的BET比表面积为200-450m2/g，孔容为0.50-1.50cm3/g。
本发明的钛改性大孔氧化铝的制备方法，包括如下内容：
（1）将胶溶剂缓慢加入到勃姆石悬浊液中，然后升温老化一定时间，得到澄清的铝溶胶；
（2）将铝溶胶、无机铝盐、甲醇钛、聚乙二醇、酰胺类化合物和低碳醇水溶液混合均匀，然后再加入环氧丙烷和/或吡啶，混合均匀得到凝胶；
（3）将步骤（2）的凝胶进行老化，得到老化产物，然后经低碳醇水溶液浸泡、固液分离，固相经干燥和焙烧，得到钛改性大孔氧化铝。
本发明方法中，步骤（1）所述的勃姆石悬浊液的固含量1wt%-15wt%，勃姆石悬浊液一般是将勃姆石粉均匀分散于水中得到。
本发明方法中，步骤（1）在搅拌条件下进行，所述的老化通过加热回流的方式，回流温度70℃-95℃，回流时间1-12小时。
本发明方法中，步骤（1）所述的胶溶剂为铝溶胶制备过程中常用胶溶剂，可以为盐酸、硝酸、硫酸、甲酸或乙酸中的一种或多种。步骤（1）所述的胶溶剂以H+计与勃姆石粉以Al计的摩尔比0.05-1.0。
本发明方法中，以步骤（2）物料体系重量为基准，低碳醇水溶液的加入量为10wt%-80wt%，无机铝盐的加入量为5wt%-30wt%，铝溶胶加入量为1wt%-10wt%，优选为0.2wt%-1.5wt%，聚乙二醇的加入量为0.1wt%-3.0wt%，优选为0.2wt%-2.0 wt%。其中，低碳醇水溶液中水与低碳醇的质量比为1.0-1.5；酰胺类化合物含量为0.1wt%-5.0wt%；在制备体系中，甲醇钛中的钛元素与体系中的铝元素，折算成TiO2与Al2O3后，二氧化钛含量为0.5wt%-45wt%，优选为1wt%-30wt%。环氧丙烷和/或吡啶与Al3+（不包含铝溶胶中的Al）的摩尔比为1.5-9.5，优选为3.0-7.5。环氧丙烷和吡啶二者可任意比例混合。
本发明方法中，聚乙二醇的粘均分子量为10000-3000000，优选为100000-2000000。
本发明方法中，步骤（2）所述的各种物料的加入顺序不加以特殊限制，其中低碳醇水溶液中的低碳醇和水可以分开加入，优选为：水、低碳醇、无机铝盐、甲醇钛、聚乙二醇、铝溶胶、含酰胺基团的化合物依次加入。一般在后一种物料加入前，需要将先前加入的物料混合均匀。
本发明方法中，步骤（2）所述的无机铝盐是硝酸铝、氯化铝或硫酸铝中的一种或多种。
本发明方法中，所述的低碳醇为C5以下的醇，优选为甲醇、乙醇、正丙醇和异丙醇中的一种或多种，最好为乙醇和/或丙醇。
本发明方法中，步骤（2）所述的酰胺类化合物可以为甲酰胺、乙酰胺、N，N-二甲基甲酰胺、N-甲基乙酰胺、苯甲酰胺或2-苯乙酰胺中的一种或多种。
本发明方法中，步骤（3）所述的老化条件为：20-80℃下老化12-120小时。
本发明方法中，步骤（3）所述的浸泡条件为：浸泡温度10-80℃，浸泡时间为12-60小时；所述的浸泡所用的低碳醇水溶液，其质量浓度不小于50wt%。
本发明方法中，步骤（3）中所述的干燥，为普通常压干燥，干燥温度不大于60℃，优选为20-40℃，干燥至产物不再发生明显的减重。所述的焙烧是在400-700℃焙烧1-24小时，优选为500-650℃焙烧2-12小时。
本发明通过向制备体系中引入铝溶胶晶种可以诱导氧化铝前驱物由非晶态前体向晶态前体演化，从而在较低的焙烧温度下即可容易地转变为γ晶态，可显著节省能耗。本发明酰胺类化合物的加入可以抑制超大孔的生成，使大孔更加均匀集中，有利于消除孔道尺寸不均匀带来的应力作用，此外通过控制反应条件，本发明制备的大孔氧化铝的大孔孔壁与大孔孔径的尺寸相比较，两者相当或前者大于后者，相对较厚的孔壁使材料具有较高的压碎强度，可以更好地满足工业上苛刻的应用要求。本发明中采用的钛的前驱物为甲醇钛，在含有大量的低碳醇反应体系中与其它组分混溶性良好，不易水解生成大颗粒二氧化钛，且体系pH呈酸性，可以形成均相凝胶，因此能够均匀地掺杂在最终的氧化铝体相中。
本发明所述的大孔氧化铝可以用作多相催化剂的载体，应用于各类大分子催化反应，如加氢反应、烷基化反应以及水处理过程中污染物的吸附、降解等。
附图说明
图1为实施例1制备的大孔氧化铝的扫描电镜图像。
图2为实施例1制备的大孔氧化铝的XRD图谱。
图3为实施例1制备的大孔氧化铝的体相局部的钛元素STEM-EDS-MAPPING分布图。
具体实施方式
下面结合实施例对本发明作进一步详细说明。本发明中，以扫描电镜观察大孔的及其贯通情况。晶态采用XRD法测试。所述大孔氧化铝的孔隙率及平均孔径以压汞法表征测试。载体的机械强度以侧压强度表示，侧压强度采用大连鹏辉科技开发有限公司生产的DL2型强度仪进行测试。勃姆石粉采用市场销售的产品或自制。钛含量材料XRF法测量，钛体相分散均匀性采用场发射超高分辨透射电镜STEM-EDS-MAPPING法表征，测试中随机选取样品10个位置，做钛元素EDS-MAPPING 图，图中代表钛元素分布的亮点的尺寸代表了钛元素团簇尺寸及分布均匀性，相邻元素团簇的平均距离不超过30 nm视为均匀分布。本发明的钛元素以二氧化钛的形式存在于体相中，所述钛元团簇尺寸不等同于二氧化钛颗粒尺寸，但钛元团簇尺寸越大则二氧化钛颗粒或聚集物尺寸越大，钛元团簇分布越均匀则二氧化钛分布越均匀。
实施例1
铝溶胶的制备：勃姆石粉与蒸馏水混合形成悬浊液（固含量3wt%），在连续搅拌的条件下，滴加盐酸，满足酸/铝摩尔比0.07，滴加完毕升温至85℃回流5小时形成澄清的铝溶胶。
室温下（约25℃）将水、无水乙醇、氯化铝、甲醇钛、聚乙二醇、铝溶胶、甲酰胺混合均匀，再加入吡啶，混合物各组分以重量计，含量分别为：水22wt%，乙醇20wt%，氯化铝21wt%，甲醇钛5wt%，聚乙二醇（粘均分子量100万）1.0wt%，铝溶胶1wt%，甲酰胺1.0wt%，吡啶29%。混合均匀之后，所得凝胶于40℃下老化48小时，然后用75wt%的乙醇水溶液浸泡老化后的混合物48小时，浸泡完毕并除去液相后，在40℃下烘干直至产物不再发生明显的减重。然后在550℃下焙烧3小时，然后冷却到室温，得到所述的大孔氧化铝。经XRD测试，具有良好的γ晶态，总孔隙率为81%，大孔分布均匀，具有三维立体空间上的贯通性，大孔孔径242nm，大孔孔隙率占67%，大孔壁厚与孔径尺寸比值为2.1，侧压强度15N/mm，BET比表面积为367m2/g，孔容为0.61cm3/g。二氧化钛含量为27.4wt%，场发射超高分辨透射电镜STEM-EDS-MAPPING显示钛元素在氧化铝体相上的团簇尺寸约1.6nm，且分布均匀。
实施例2
铝溶胶的制备同实施例1。
室温下（约25℃）将水、无水乙醇、氯化铝、甲醇钛、聚乙二醇、铝溶胶、乙酰胺混合均匀，再加入环氧丙烷，混合物各组分以重量计，含量分别为：水21wt%，乙醇20wt%，氯化铝20wt%，甲醇钛7wt%，聚乙二醇（粘均分子量150万）1wt%，铝溶胶1wt%，乙酰胺1.0wt%，环氧丙烷29wt%。混合均匀之后，所得凝胶于40℃下老化72小时，然后用乙醇浸泡老化后的混合物72小时，浸泡完毕并除去液相后，在40℃下烘干直至产物不再发生明显的减重。然后在550℃下焙烧5小时，然后冷却到室温，得到所述的大孔氧化铝。经XRD测试，具有良好的γ晶态，总孔隙率为84%，大孔分布均匀，具有三维立体空间上的贯通性，大孔孔径194nm，大孔孔隙率占85%，大孔壁厚与孔径尺寸比值为1.9，侧压强度21N/mm，BET比表面积为370m2/g，孔容为0.79cm3/g。二氧化钛含量为33.1wt%，场发射超高分辨透射电镜STEM-EDS-MAPPING显示钛元素在氧化铝体相上的团簇尺寸约1.4nm，且分布均匀。
实施例3
铝溶胶的制备：勃姆石粉与蒸馏水混合形成悬浊液（固含量1.5wt%），在连续搅拌的条件下，滴加乙酸，满足酸/铝摩尔比0.15，滴加完毕升温至90℃回流8小时形成澄清的溶胶。
室温下（约25℃）将水、无水乙醇、氯化铝、甲醇钛、聚乙二醇、铝溶胶、N，N-二甲基甲酰胺混合均匀，再加入吡啶，混合物各组分以重量计，含量分别为：水21wt%，乙醇20wt%，氯化铝24wt%，甲醇钛4wt%，聚乙二醇（粘均分子量100万）1wt%，铝溶胶1wt%，N，N-二甲基甲酰2wt%，吡啶27wt%。混合均匀之后，所得凝胶于40℃下老化48小时，然后用80wt%乙醇水溶液浸泡老化后的混合物72小时，浸泡完毕并除去液相后，在40℃下烘干直至产物不再发生明显的减重。然后在700℃下焙烧2.5小时，然后冷却到室温，得到所述的大孔氧化铝。经XRD测试，具有良好的γ晶态，总孔隙率为77%，大孔分布均匀，具有三维立体空间上的贯通性，大孔孔径153nm，大孔孔隙率占87%，大孔壁厚与孔径尺寸比值为3.4，侧压强度26N/mm，BET比表面积为391m2/g，孔容为0.91cm3/g。氧化钛含量为20wt%，场发射超高分辨透射电镜STEM-EDS-MAPPING显示钛元素在氧化铝体相上的团簇尺寸约0.9nm，且分布均匀。
对比例1
按照“应用化工，2016，45（9）：1788-1802”的方法制备钛改性复合氧化铝。该法采用超增容法，制备体系具有一定的危险性，复合产物中钛元素分布不太均匀。
对比例2
按照“无机盐工业，2018，50（3）：74-76”的方法制备钛改性氧化铝，所得产品无明显的三维大孔结构。
对比例3
按照CN99113284.X的方法制备钛改性氧化铝，所用氧化钛前驱体易水解生成二氧化钛团聚，致使钛元素在复合体中分布不均匀，制备过程也形成较多的氯离子。
Claims (16)
1.一种钛改性大孔氧化铝，其特征在于：大孔氧化铝为γ晶态，总孔隙率60%-85%，所述的大孔孔径为100-1000nm，大孔占总孔隙率的比例为40%-90%；大孔分布均匀且三维贯通；大孔壁厚与孔径尺寸比值为0.5-4.5；侧压破碎强度为8-30N/mm；钛元素以二氧化钛形式在氧化铝体相均匀分散，钛元素团簇尺寸在0.5nm以上且小于2.5nm。
2.根据权利要求1所述的钛掺杂γ-氧化铝，其特征在于：以钛掺杂γ-氧化铝总重量为基准，钛元素以二氧化钛计含量为0.5wt%-45wt%。
3.根据权利要求1所述的钛掺杂γ-氧化铝，其特征在于：钛掺杂γ-氧化铝的BET比表面积为200-450m2/g，孔容为0.50 -1.50cm3/g。
4.一种权利要求1~3任一所述的钛改性大孔氧化铝的制备方法，其特征在于：包括如下内容：（1）将胶溶剂缓慢加入到勃姆石悬浊液中，然后升温老化一定时间，得到澄清的铝溶胶；（2）将铝溶胶、无机铝盐、甲醇钛、聚乙二醇、酰胺类化合物和低碳醇水溶液混合均匀，然后再加入环氧丙烷和/或吡啶，混合均匀得到凝胶；（3）将步骤（2）的凝胶进行老化，得到老化产物，然后经低碳醇水溶液浸泡、固液分离，固相经干燥和焙烧，得到钛改性大孔氧化铝。
5.根据权利要求4所述的方法，其特征在于：步骤（1）所述的勃姆石悬浊液的固含量1wt%-15wt%。
6.根据权利要求4所述的方法，其特征在于：步骤（1）在搅拌条件下进行，所述的老化通过加热回流的方式，回流温度70℃-95℃，回流时间1-12小时。
7.根据权利要求4所述的方法，其特征在于：步骤（1）所述的胶溶剂为为盐酸、硝酸、硫酸、甲酸或乙酸中的一种或多种；所述的胶溶剂以H+计与勃姆石粉以Al计的摩尔比0.05-1.0。
8.根据权利要求4所述的方法，其特征在于：以步骤（2）物料体系重量为基准，低碳醇水溶液的加入量为10wt%-80wt%，无机铝盐的加入量为5wt%-30wt%，铝溶胶加入量为1wt%-10wt%，聚乙二醇的加入量为0.1wt%-3.0wt%；其中，低碳醇水溶液中水与低碳醇的质量比为1.0-1.5；酰胺类化合物含量为0.1wt%-5.0wt%；聚乙二醇的粘均分子量为10000-3000000。
9.根据权利要求4所述的方法，其特征在于：其特征在于：环氧丙烷和/或吡啶与Al3+的摩尔比为1.5-9.5，不包含铝溶胶中的Al。
10.根据权利要求4所述的方法，其特征在于：步骤（2）所述的无机铝盐是硝酸铝、氯化铝或硫酸铝中的一种或多种。
11.根据权利要求4所述的方法，其特征在于：所述的低碳醇为甲醇、乙醇、正丙醇和异丙醇中的一种或多种。
12.根据权利要求4所述的方法，其特征在于：步骤（2）所述的酰胺类化合物为甲酰胺、乙酰胺、N，N-二甲基甲酰胺、N-甲基乙酰胺、苯甲酰胺或2-苯乙酰胺中的一种或多种。
13.根据权利要求4所述的方法，其特征在于：步骤（3）所述的老化条件为：20-80℃下老化12-120小时。
14.根据权利要求4所述的方法，其特征在于：步骤（3）所述的浸泡条件为：浸泡温度10-80℃，浸泡时间为12-60小时；所述的浸泡所用的低碳醇水溶液，其质量浓度不小于50wt%。
15.根据权利要求4所述的方法，其特征在于：所述的焙烧是在400-700℃焙烧1-24小时。
16.一种权利要求1~3任一所述的钛改性大孔氧化铝在加氢反应、烷基化反应以及水处理过程中污染物的吸附、降解中的应用。
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