CN110935433B - Silicon modified macroporous alumina and preparation method thereof - Google Patents
Silicon modified macroporous alumina and preparation method thereof Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 49
- 239000010703 silicon Substances 0.000 title claims abstract description 49
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 44
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- -1 silicon alkoxide Chemical class 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 16
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 14
- 229910001593 boehmite Inorganic materials 0.000 claims description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000013507 mapping Methods 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000523 sample 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-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 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims 1
- 239000000356 contaminant Substances 0.000 claims 1
- 238000010586 diagram Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 235000019441 ethanol Nutrition 0.000 description 25
- 239000000047 product Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 8
- 239000004964 aerogel Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect 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
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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
- 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
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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Abstract
The invention discloses silicon modified macroporous alumina and a preparation method thereof, wherein the alumina has the following properties: the macroporous alumina is gamma crystalline state, the total porosity is 60-85%, the pore diameter of the macropore is 100-1000nm, and the proportion of the macropore in the total porosity is 40-75%; the macropores are uniformly distributed and are communicated in a three-dimensional way; the ratio of the wall thickness of the large hole to the aperture size is 0.7-3.0; the lateral pressure strength is 8-25N/mm, the silicon element is uniformly dispersed and doped in the alumina phase, and the silicon content is 0.5-15 wt%. The macroporous alumina has three-dimensional connectivity and high mechanical strength, can meet the strength requirement of the existing heterogeneous catalytic reaction, and can be used as a good carrier of a catalyst.
Description
Technical Field
The invention relates to silicon modified macroporous alumina and a preparation method thereof, belonging to the field of inorganic material preparation.
Background
The activated alumina is used as a good hydrogenation catalytic carrier material and has wide application in the oil refining industry. An activated alumina support with excellent performance requires not only good pore structure properties but also good surface properties. The larger pore channel structure is beneficial to mass transfer of reaction materials and improves the reaction efficiency, and the appropriate surface property plays an important role in the reaction performance of the catalyst.
In the report of physical chemistry, 2005, 21 (02) '221-224 preparation of Al2O3 bulk aerogel by normal pressure drying method', aluminum nitrate is taken as a precursor, ethanol is taken as a solvent, formamide is taken as a drying control chemical additive, propylene oxide is taken as a gel network inducer, alumina gel is prepared by a sol-gel method, and light and bulk alumina aerogel with concentrated mesopore distribution is obtained under the drying condition of normal pressure. But the mesopores of the aerogel material are less than 20nm, and macropores with the size of more than 100nm are not contained; meanwhile, pure ethanol is used as a solvent, and one of the purposes is to keep the block system as far as possible from shrinking during drying under normal pressure, which also results in the aerogel material having low density and weak mechanical strength. Therefore, the block aerogel material is not suitable for the heterogeneous catalysis field of the petrochemical industry in terms of pore size distribution and mechanical strength.
CN 1184078A adopts aluminium hydroxide produced by parallel-flow gelling as seed crystal, and utilizes the oscillation of pH value to control the growth and size of alumina crystal grains, so that larger pore channels are formed among the crystal grains. However, the method has limited overall pore-forming effect, the obtained pore size is generally less than 100nm, the distribution of macropores is dispersed, and the connectivity is weak.
In US 4448896, US 4102822 and EP 0237240, carbon black, starch and carbon fiber are used as pore-enlarging agents to prepare macroporous alumina, the dosage of the used physical pore-enlarging agent is more than 10wt% of alumina, the method is to add the physical pore-enlarging agent into the alumina precursor, the dosage of the pore-enlarging agent is large, the formed macropores are distributed and dispersed, the macropore pore channel is in an ink bottle shape, the pore opening is small, the pore channel can not form a continuous through-pore channel, and the mass transfer effect on macromolecules is poor.
CN 201010221297.6 discloses a preparation method of integral macroporous alumina. The method comprises the following steps: uniformly mixing an aluminum source, polyethylene glycol and at least one selected from low-carbon alcohol and water, adding alkylene oxide into the mixture, aging, soaking, drying and roasting to obtain the integral macroporous alumina with the pore diameter of 0.05-10 microns (50-10000 nm). The method mainly controls the formation of macropores and the pore diameter thereof by taking the content of polyethylene glycol as a main component, and although macropores with the size of 50nm-10000nm can be obtained, the method has the following defects: (1) Macropores with the diameter of more than 1 mu m can be generated more easily, macropores with the diameter of less than 1 mu m can be controlled more easily, and macropores with the diameter of more than 1 mu m are obtained in the practical preparation of the embodiment; (2) The obtained macro-pores have isolated appearance and poor spatial continuity, and are not beneficial to mass transfer of macromolecules; (3) The resulting material forms amorphous, macroporous alumina at relatively low firing temperatures (550-650 c), which is detrimental to catalytic applications.
Modern chemical engineering, 2011, 31 (3): 46-48+50 'preparation and characterization of three-dimensional ordered macroporous alumina with mesoporous pore walls', the three-dimensional ordered macroporous alumina is prepared by polystyrene microspheres, the pore walls are thin, and the mechanical strength is extremely weak.
The above techniques mainly relate to the role of the alumina channels, but do not consider the effect of the modification of the material and its surface properties on the catalysis. The surface of the alumina has acidity, but the traditional alumina only has L acid sites, and the surface of the alumina generates B acid sites on the basis of keeping L acid by adopting a proper modification method, thereby being beneficial to improving the catalytic performance of the catalytic material.
CN201510213566.7 the present invention provides a method for preparing silicon modified alumina, and a product and an application thereof. Reacting alumina with tetraethoxysilane in an alkaline environment to obtain the silicon modified alumina material. However, in an alkaline environment, tetraethoxysilane is easy to hydrolyze and precipitate, is difficult to uniformly act with alumina, and cannot form homogeneous doping. CN201611126412.5 first peptizes an alumina precursor into a sol, then adds silica sol, and after mixing and dissolution, carries out subsequent treatment on the silica-modified alumina. Because the properties of the aluminum sol and the silica sol are completely different, the aluminum sol and the silica sol are easy to be coagulated when being mixed and dissolved, a homogeneous system is difficult to generate, and the uniformly doped silicon modified alumina is difficult to form.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides silicon modified macroporous alumina and a preparation method thereof. The macropores of the macroporous alumina are three-dimensionally communicated, the material has high mechanical strength, can meet the strength requirement of the existing heterogeneous catalytic reaction, and can be used as a good carrier of a catalyst.
The silicon modified macroporous alumina has the following properties: the macroporous alumina is gamma crystalline state, the total porosity is 60-85%, the pore diameter of the macropore is 100-1000nm, and the proportion of macropores in the total porosity is 40-75%, preferably 50-70%; the macropores are uniformly distributed and are communicated in a three-dimensional way; the ratio of the wall thickness of the large hole to the aperture size is 0.7-3, preferably 1-2; the lateral pressure crushing strength is 8-25N/mm, preferably 10-20N/mm. According to the silicon modified macroporous alumina, silicon elements are uniformly distributed in an alumina bulk phase, and the silicon content is 0.5-15 wt%, preferably 1-10 wt%; the molar ratio of L acid to B acid is 0.5-12, preferably 1.0-8.0.
The BET specific surface area of the silicon modified macroporous alumina is 200-480m 2 Per g, pore volume of 0.40-1.80cm 3 /g。
The preparation method of the silicon modified macroporous alumina comprises the following steps:
(1) Slowly adding a peptizing agent into the boehmite suspension, and then heating and aging for a certain time to obtain clear aluminum sol;
(2) Uniformly mixing the aluminum sol, inorganic aluminum salt, silicon alkoxide, polyethylene glycol and lower alcohol aqueous solution of amide compounds, then adding propylene oxide and/or pyridine, and uniformly mixing to obtain gel;
(3) And (3) aging the gel obtained in the step (2) to obtain an aged product, then soaking the aged product in a low-carbon alcohol aqueous solution, performing solid-liquid separation, and drying and roasting a solid phase to obtain the silicon-modified macroporous alumina.
In the method of the present invention, the solid content of the boehmite suspension described in the step (1) is 1wt% to 15wt%, and the boehmite suspension is generally obtained by uniformly dispersing boehmite powder in water.
In the method, the step (1) is carried out under the condition of stirring, and the aging is carried out in a heating reflux mode, wherein the reflux temperature is 70-95 ℃, and the reflux time is 1-12 hours.
In the method, the peptizing agent in the step (1) is a commonly used peptizing agent in the preparation process of the aluminum sol, and can be one or more of hydrochloric acid, nitric acid, sulfuric acid, formic acid or acetic acid. The peptizing agent in the step (1) is H + The molar ratio of the boehmite powder to the boehmite powder in terms of Al is 0.05-1.
In the method, the weight of the material system in the step (2) is taken as the reference, the adding amount of the lower alcohol aqueous solution is 10-80 wt%, the adding amount of the inorganic aluminum salt is 5-30 wt%, and the silicon alkoxide is addedThe adding amount is 1 to 10 weight percent, the adding amount of the aluminum sol is 1 to 10 weight percent, and the adding amount of the polyethylene glycol is 0.1 to 3.0 weight percent, and the optimized adding amount is 0.2 to 2.0 weight percent. Wherein the mass ratio of water to the low-carbon alcohol in the low-carbon alcohol aqueous solution is 1.0-1.5; the content of the amide compound is 0.1-5.0 wt%; propylene oxide and/or pyridine with Al 3+ (not including Al in the alumina sol) in a molar ratio of 1.5 to 9.5, preferably 3.0 to 7.5. The propylene oxide and pyridine may be mixed in any proportion.
In the method of the present invention, the viscosity average molecular weight of the polyethylene glycol is 10000 to 3000000, preferably 100000 to 2000000.
In the method of the present invention, the order of adding the materials in step (2) is not particularly limited, wherein the lower alcohol and water in the lower alcohol aqueous solution may be added separately, preferably: water, low carbon alcohol, inorganic aluminum salt, silicon alkoxide, polyethylene glycol, alumina sol and amide compounds are added in sequence. Generally, before the latter material is added, the material added previously needs to be mixed uniformly.
In the method of the present invention, the inorganic aluminum salt in step (2) is one or more of aluminum nitrate, aluminum chloride or aluminum sulfate.
In the method of the invention, the silicon alkoxide in the step (2) is methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or a mixture of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate in any proportion.
In the process of the present invention, the lower alcohol is generally C 5 The alcohol is preferably one or more of methanol, ethanol, n-propanol and isopropanol, and preferably ethanol and/or propanol.
In the method of the present invention, the amide compound in step (2) may be one or more of formamide, acetamide, N-dimethylformamide, N-methylacetamide, benzamide, or 2-phenylacetamide.
In the method of the invention, the aging conditions in the step (3) are as follows: aging at 20-80 deg.C for 12-120 hr.
In the method, the soaking conditions in the step (3) are as follows: the soaking temperature is 10-80 ℃, and the soaking time is 12-60 hours; the mass concentration of the low-carbon alcohol aqueous solution used for soaking is not less than 50wt%.
In the method, the drying in the step (3) is ordinary normal pressure drying, the drying temperature is not more than 60 ℃, and preferably 20-40 ℃, and the drying is carried out until the product does not obviously lose weight any more. The roasting is carried out at 400-700 ℃ for 1-24 hours, preferably 500-650 ℃ for 2-12 hours.
The invention can induce the evolution of the aluminum oxide precursor from the amorphous precursor to the crystalline precursor by introducing the alumina sol seed crystal into the preparation system, thereby being easily converted into the gamma crystalline state at lower roasting temperature and obviously saving energy consumption. The introduction of the alumina sol crystal seed ensures that the wall of the macroporous hole generates a large amount of particles, and the wall of the macroporous hole is changed from a smooth compact state into a particle aggregate, which is beneficial to generating particle pores and improving the specific surface area of the material, thereby enlarging the contact area of the reaction material and the catalyst to improve the reaction activity. The addition of the amide compound can inhibit the generation of ultra-large pores, so that the large pores are more uniformly concentrated, and the stress effect caused by nonuniform pore sizes is favorably eliminated. The precursor of silicon adopted in the invention is silicon alkoxide, which has good miscibility with other components in a reaction system containing a large amount of lower alcohol, and the pH of the system is acidic, so that homogeneous gel can be formed, and the precursor can be uniformly doped in the final alumina bulk phase.
The macroporous alumina can be used as a carrier of a heterogeneous catalyst and applied to various macromolecular catalytic reactions, such as hydrogenation reaction, alkylation reaction, pollutant adsorption and degradation in the water treatment process and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the macroporous alumina prepared in example 1.
Figure 2 is an XRD pattern of the macroporous alumina prepared in example 1.
FIG. 3 is a MAPPING profile of the bulk local silicon element of the macroporous alumina prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples. In the present invention, the large pore and the penetration thereof are observed by a scanning electron microscope. The crystalline state was tested by XRD. The porosity and the average pore diameter of the macroporous alumina are characterized and tested by a mercury intrusion method. The mechanical strength of the carrier was expressed as lateral pressure strength, which was measured using a DL2 type strength meter produced by the university linkage penghy scientific and technological development ltd. The boehmite powder is a product sold in the market or manufactured by self. The XRF method measurement of the silicon content material is carried out, the silicon bulk phase dispersion uniformity is characterized by adopting an EDS element distribution MAPPING method of an electronic probe, 10 positions of a sample are randomly selected in the test, a silicon element MAPPING graph is made, the maximum distance between bright spots representing silicon elements in the graph is not more than 30nm, and the silicon elements are considered to be uniformly distributed in the area. The acidity measurement was carried out by IR method.
Example 1
Preparing aluminum sol: mixing boehmite powder and distilled water to form a suspension (solid content is 3 wt%), dropwise adding hydrochloric acid under the condition of continuous stirring to meet the acid/aluminum molar ratio of 0.07, and heating to 85 ℃ after the dropwise adding, and refluxing for 5 hours to form clear aluminum sol.
Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, ethyl orthosilicate, polyethylene glycol, alumina sol and formamide at room temperature (about 25 ℃), and then adding pyridine, wherein the weight percentages of the components of the mixture are respectively: 22% of water, 20% of ethanol, 20% of aluminum chloride, 4% of ethyl orthosilicate, 0.5% of polyethylene glycol (viscosity average molecular weight is 100 ten thousand), 2% of alumina sol, 1.5% of formamide and 30% of pyridine. After mixing uniformly, the gel obtained is aged for 48 hours at 40 ℃, then the aged mixture is soaked for 48 hours by 70wt% of ethanol water solution, after soaking is finished and liquid phase is removed, and the gel is dried at 40 ℃ until the product is not reduced obviously any more. Then calcined at 550 ℃ for 3 hours and then cooled to room temperature to obtain the macroporous alumina. XRD test shows that the crystal has excellent gamma crystalline state, total porosity of 84%, homogeneous macroporous distribution, three-dimensional connectivity, macroporous diameter of 470nm, macroporous porosity of 66%, and large pore sizeThe inch ratio was 0.9, the lateral pressure strength was 17N/mm, and the BET specific surface area was 374m 2 Per g, pore volume of 0.68cm 3 (iv) g. The silicon content was 13.8wt%, and the electron probe EDS-MAPPING showed that the silicon element was uniformly distributed in the alumina phase. The molar ratio of L acid/B acid of the material was 1.5.
Example 2
The preparation of the aluminum sol was the same as in example 1.
Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, tetraethoxysilane, polyethylene glycol, alumina sol and acetamide at room temperature (about 25 ℃), and then adding propylene oxide, wherein the mixture comprises the following components in parts by weight: 22% of water, 20% of ethanol, 20% of aluminum chloride, 5% of ethyl orthosilicate, 1% of polyethylene glycol (with the viscosity average molecular weight of 150 ten thousand), 1% of alumina sol, 1.0% of acetamide and 30% of propylene oxide. After uniform mixing, the gel obtained is aged for 72 hours at 40 ℃, then the aged mixture is soaked for 72 hours by ethanol, and after the soaking is finished and the liquid phase is removed, the gel is dried at 40 ℃ until the product does not lose weight obviously any more. Then roasting at 450 ℃ for 5 hours, and then cooling to room temperature to obtain the macroporous alumina. XRD test shows that the material has excellent gamma crystalline state, total porosity of 84%, homogeneous macroporous distribution, three-dimensional connectivity, macroporous size of 240nm, macroporous porosity of 74%, wall thickness and size ratio of 1.7, side pressure strength of 15N/mm, BET specific surface area of 401m 2 Per g, pore volume of 0.74cm 3 (ii) in terms of/g. The silicon content was 12.1wt%, and the electron probe EDS-MAPPING showed that the silicon element was uniformly distributed in the alumina phase. The molar ratio of L acid/B acid of the material was 1.8.
Example 3
Preparing aluminum sol: mixing boehmite powder and distilled water to form a suspension (solid content is 1.5 wt%), dropwise adding acetic acid under the condition of continuous stirring to meet the acid/aluminum molar ratio of 0.15, and heating to 90 ℃ after the dropwise addition, and refluxing for 8 hours to form a clear sol.
Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, propyl orthosilicate, polyethylene glycol, alumina sol and N, N-dimethylformamide at room temperature (about 25 ℃), and then adding pyridine, wherein the weight percentages of the components of the mixture are respectively as follows: 21% of water, B20% of alcohol, 22% of aluminum chloride, 3% of propyl orthosilicate, 1% of polyethylene glycol (viscosity average molecular weight is 100 ten thousand), 3% of alumina sol, 2% of N, N-dimethylformamide and 28% of pyridine. After uniform mixing, the gel obtained is aged for 48 hours at 40 ℃, then the aged mixture is soaked for 72 hours by 90wt% ethanol water solution, and after the soaking is finished and the liquid phase is removed, the gel is dried at 40 ℃ until the product is not obviously reduced. Then roasting at 700 ℃ for 2.5 hours, and then cooling to room temperature to obtain the macroporous alumina. XRD test shows that the material has excellent gamma crystalline state, total porosity of 74%, homogeneous macroporous distribution, three-dimensional penetration, 184nm macroporous diameter, 86% macroporous porosity, wall thickness and size ratio of 1.9, side pressure strength of 22N/mm, BET specific surface area of 451m 2 Per g, pore volume 1.01cm 3 (iv) g. The silicon content was 6wt%, and the electron probe EDS-MAPPING showed that the silicon element was uniformly distributed on the alumina phase. The molar ratio of L acid/B acid of the material was 3.1.
Comparative example 1
This example is compared with example 1. Except that the weight of the alumina sol (seed) was not added and was replaced by equal amounts of ethanol and water.
Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, polyethylene glycol and formamide at room temperature (about 25 ℃), and then adding propylene oxide, wherein the mixture comprises the following components in parts by weight: 21% of water, 21% of ethanol, 23% of aluminum chloride, 0.5% of polyethylene glycol (viscosity average molecular weight is 100 ten thousand), 2% of alumina sol, 2.0% of formamide and 30.5% of pyridine. After uniform mixing, the obtained gel is aged for 48 hours at 40 ℃, then the aged mixture is soaked for 48 hours by using a mixed solution of ethanol and water, and after the soaking is finished and a liquid phase is removed, the gel is dried at 40 ℃ until the product is not obviously reduced. Then calcined at 450 ℃ for 5 hours and then cooled to room temperature to obtain the macroporous alumina. The product is amorphous by XRD test.
Comparative example 2
This example is compared with example 1. Except that no silicon source is introduced, and the weight of the silicon source is replaced by equal amount of ethanol and water. The resulting sample was tested by IR method and contained no B acid.
Comparative example 3
Alumina aerogels were prepared according to the Proc. Physico-chemical report, 2005, 21 (02): 221-224, and the products obtained had no significant macropores and a lateral pressure strength of 0.2N/mm.
Comparative example 4
In "modern chemical industry, 2011, 31 (3): 46-48+ 50' of three-dimensional ordered macroporous alumina, the pore wall is thin, the ratio of the pore wall to the pore diameter is about 0.1, and the lateral pressure strength is 1N/mm.
Comparative example 5
Silicon modified alumina was prepared in the method of CN 201510213566.7. The obtained material does not contain three-dimensionally through macropores, and the distribution of silicon on the alumina phase is very uneven.
Claims (19)
1. A silicon modified macroporous alumina is characterized in that: the macroporous alumina is gamma crystalline state, the total porosity is 60-85%, the pore diameter of the macropore is 100-1000nm, and the proportion of the macropore in the total porosity is 40-75%; the macropores are uniformly distributed and are communicated in a three-dimensional way; the ratio of the wall thickness to the pore diameter of the large pore is 0.7-3; the lateral pressure strength is 8-25N/mm; the silicon element is uniformly distributed in the alumina body phase, the silicon content is 0.5wt% -15wt%, and the molar ratio of the L acid to the B acid is 0.5-12;
the EDS element distribution MAPPING method of the electronic probe is characterized in that the maximum distance between bright spots of any adjacent silicon element distribution in an EDS-MAPPING diagram is not more than 30nm;
the silicon modified macroporous alumina is prepared by the following method: (1) Slowly adding a peptizing agent into the boehmite suspension, and then heating and aging for a certain time to obtain clear aluminum sol; (2) Uniformly mixing the aluminum sol, inorganic aluminum salt, silicon alkoxide, polyethylene glycol and lower alcohol aqueous solution of amide compounds, then adding propylene oxide and/or pyridine, and uniformly mixing to obtain gel; (3) And (3) aging the gel obtained in the step (2) to obtain an aged product, then soaking the aged product in a low-carbon alcohol aqueous solution, performing solid-liquid separation, and drying and roasting a solid phase to obtain the silicon-modified macroporous alumina.
2. The silicon-modified macroporous alumina of claim 1, wherein: the molar ratio of the L acid to the B acid is 1.0-8.0.
3. The silicon-modified macroporous alumina of claim 1, wherein: the BET specific surface area of the macroporous alumina is 200-480m 2 Per g, pore volume of 0.40-1.80cm 3 /g。
4. A method for preparing the silicon modified macroporous alumina of claim 1, comprising the steps of: (1) Slowly adding a peptizing agent into the boehmite suspension, and then heating and aging for a certain time to obtain clear aluminum sol; (2) Uniformly mixing the aluminum sol, inorganic aluminum salt, silicon alkoxide, polyethylene glycol and lower alcohol aqueous solution of amide compounds, then adding propylene oxide and/or pyridine, and uniformly mixing to obtain gel; (3) And (3) aging the gel obtained in the step (2) to obtain an aged product, then soaking the aged product in a low-carbon alcohol aqueous solution, performing solid-liquid separation, and drying and roasting a solid phase to obtain the silicon-modified macroporous alumina.
5. The method of claim 4, wherein: the solid content of the boehmite suspension in the step (1) is 1-15 wt%.
6. The method of claim 4, wherein: the step (1) is carried out under the condition of stirring, and the aging is carried out in a heating reflux mode, wherein the reflux temperature is 70-95 ℃, and the reflux time is 1-12 hours.
7. The method of claim 4, wherein: the peptizing agent in the step (1) is one or more of hydrochloric acid, nitric acid, sulfuric acid, formic acid or acetic acid; peptizing agent with H + The mole ratio of the boehmite powder to the boehmite powder in terms of Al is 0.05-1.
8. The method of claim 4, wherein: based on the weight of the material system in the step (2), the adding amount of the lower alcohol aqueous solution is 10-80 wt%, the adding amount of the inorganic aluminum salt is 5-30 wt%, the adding amount of the silicon alkoxide is 1-10 wt%, the adding amount of the aluminum sol is 1-10 wt%, and the adding amount of the polyethylene glycol is 0.1-3.0 wt%; wherein, the content of the amide compound is 0.1wt percent to 5.0wt percent.
9. The method of claim 4, wherein: propylene oxide and/or pyridine with Al 3+ Is 1.5 to 9.5, does not contain Al in the alumina sol; the propylene oxide and the pyridine are mixed in any proportion.
10. The method of claim 4, wherein: the mass ratio of water to the low-carbon alcohol in the low-carbon alcohol aqueous solution is 1.0-1.5.
11. The method of claim 4, wherein: the viscosity average molecular weight of polyethylene glycol is 10000-3000000.
12. The method of claim 4, wherein: the inorganic aluminum salt in the step (2) is one or more of aluminum nitrate, aluminum chloride or aluminum sulfate.
13. The method of claim 4, wherein: the silicon alkoxide in the step (2) is one or more of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate.
14. The method of claim 4, wherein: the lower alcohol is one or more of methanol, ethanol, n-propanol and isopropanol.
15. The method of claim 4, wherein: the amide compound in the step (2) is one or more of formamide, acetamide, N-dimethylformamide, N-methylacetamide, benzamide or 2-phenylacetamide.
16. The method of claim 4, wherein: the aging conditions in the step (3) are as follows: aging at 20-80 deg.C for 12-120 hr.
17. The method of claim 4, wherein: the soaking conditions in the step (3) are as follows: the soaking temperature is 10-80 ℃, and the soaking time is 12-60 hours.
18. The method of claim 4, wherein: the mass concentration of the lower alcohol aqueous solution used for soaking in the step (3) is not less than 50wt%.
19. Use of the silicon modified macroporous alumina of claim 1 in adsorption and degradation of contaminants during hydrogenation, alkylation, and water treatment.
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