CN111484057B - Alumina and preparation method and application thereof - Google Patents
Alumina and preparation method and application thereof Download PDFInfo
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- CN111484057B CN111484057B CN202010304049.1A CN202010304049A CN111484057B CN 111484057 B CN111484057 B CN 111484057B CN 202010304049 A CN202010304049 A CN 202010304049A CN 111484057 B CN111484057 B CN 111484057B
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- Prior art keywords
- monohydric alcohol
- aluminum
- water
- combination
- reaction
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 91
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 90
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 239000011148 porous material Substances 0.000 claims abstract description 48
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 230000032683 aging Effects 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000009826 distribution Methods 0.000 claims abstract description 16
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 7
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- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229960001153 serine Drugs 0.000 claims description 2
- 235000004400 serine Nutrition 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 229960002898 threonine Drugs 0.000 claims description 2
- 235000008521 threonine Nutrition 0.000 claims description 2
- 229960004441 tyrosine Drugs 0.000 claims description 2
- 235000002374 tyrosine Nutrition 0.000 claims description 2
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 2
- 229960004295 valine Drugs 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims 2
- 150000002466 imines Chemical class 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229960002989 glutamic acid Drugs 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- OFEPSGLLYPYMDB-UHFFFAOYSA-K aluminum;hexanoate Chemical compound [Al+3].CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O OFEPSGLLYPYMDB-UHFFFAOYSA-K 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 229960002743 glutamine Drugs 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical Kinetics & Catalysis (AREA)
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- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides alumina and a preparation method and application thereof. The method comprises the following steps: (1) mixing monohydric alcohol, an aluminum source and an initiator I, and reacting to obtain a monohydric alcohol aluminum solution; (2) mixing monohydric alcohol, monohydric alcohol aluminum solution and water for reaction, removing water, aging in alcohol, and performing solid-liquid separation to obtain pseudo-boehmite containing monohydric alcohol; (3) mixing pseudo-boehmite containing monohydric alcohol with an initiator II, a polymer monomer and water, heating for reaction, carrying out solid-liquid separation, and roasting the obtained solid to obtain the alumina. The preparation method provided by the invention has the advantages of simple process, low production cost and easy operation, and the obtained alumina has the characteristics of high purity, high specific surface, large pore diameter, large pore volume, concentrated pore diameter distribution and through-hole channels.
Description
Technical Field
The invention belongs to the field of metal oxide materials, and relates to a preparation method of aluminum oxide.
Background
The conventional production method of pseudo-boehmite can be divided into an organic aluminum alkoxide method and an inorganic aluminum method. The aluminum alkoxide method mainly refers to a method for producing high-quality pseudo-boehmite by taking high-purity aluminum cyclone and higher alcohols (n-amyl alcohol and n-hexyl alcohol) as raw materials, which is developed by Condea company in Germany, and the production comprises a circulating process of aluminum hydroxide, aluminum oxide, aluminum alkoxide and aluminum hydroxide. The product SB powder of the company has high purity, good crystal form, easily controlled pore structure and large specific surface area, the method becomes a main method for producing alumina carriers abroad, and the product SB powder is widely used as various catalyst carriers or binders, and the company produces more than 20 ten thousand tons every year in Brinstel and American Kchalrs factories. The japanese sumitomo chemical company has also achieved industrialization by this method, and china is still blank in this respect. And the existing aluminum alkoxide method is mainly used for synthesizing small-hole SB powder, and the synthesis of large-hole alumina is less.
CN 110395756A discloses a method for preparing large-pore-volume, multi-pore-passage and wide-distribution pseudo-boehmite, which comprises the following operation steps: (1) reacting 2N-5N aluminum raw material with alcohol under catalysis to obtain aluminum alkoxide, and preserving heat; (2) distilling and purifying, transferring the aluminum alkoxide obtained after purification to a hydrolysis reaction kettle, adding 1-8 per mill of nano-boehmite seed crystals, adding an alcohol solution, and keeping the temperature; (3) hydrolyzing, adding an auxiliary agent, and preserving heat to obtain the pseudo-boehmite product with large pore volume, multiple pore passages and wide distribution. The method adopts 2N-5N aluminum products, and meets the requirements of 1.0-1.33ml/g of pseudo-boehmite products with large pore volume and double-peak distribution multi-pore channels, the products obtained by the method have large pore volume and rich pore channels, acid addition is not easy to collapse, and the strength of the molded carrier is good, but the method has complex process and high production cost.
CN 104085908B discloses a preparation method of high-purity alumina, which comprises the following steps: (1) reacting butanol with metallic aluminum; (2) carrying out reduced pressure distillation; (3) hydrolyzing; (4) primary calcination; (5) ball milling; (6) and (4) secondary calcination. The method has the advantages that aluminum butoxide is prepared, hydrolysis and calcination are carried out, the steps are few, butanol can be repeatedly used, the purity of the prepared alumina is high, and the purity reaches 5N by adopting ICP-MS detection; the average grain diameter is small and is 0.01-0.03 mu m; the specific surface area is 3-6m2The method can improve the purity of aluminum butoxide by reduced pressure distillation, thereby improving the purity of aluminum oxide; the ion exchange resin is adopted for further impurity removal, the formation of alumina crystal grains is ensured, the purity of the alumina is improved, the preparation process is pollution-free, the energy consumption is low, and the method is green and environment-friendly and is suitable for industrial production. However, the method for synthesizing the alumina has low specific surface area and smaller pore diameter and pore volume.
Disclosure of Invention
In view of the above-mentioned disadvantages in the prior art, the present invention aims to provide an alumina, a preparation method and a use thereof. The preparation method provided by the invention can obtain macroporous high-purity alumina.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the preparation of alumina, said process comprising the steps of:
(1) mixing monohydric alcohol, an aluminum source and an initiator I, and reacting to obtain a monohydric alcohol aluminum solution;
(2) mixing monohydric alcohol, the monohydric alcohol aluminum solution obtained in the step (1) and water for reaction, removing water, aging in alcohol, and carrying out solid-liquid separation to obtain pseudo-boehmite containing monohydric alcohol;
(3) and (3) mixing the pseudo-boehmite containing the monohydric alcohol in the step (2) with an initiator II, a polymer monomer and water, heating for reaction, carrying out solid-liquid separation, and roasting the obtained solid to obtain the alumina.
According to the preparation method of the aluminum oxide, the finally formed pseudoboehmite is aged in the environment of monohydric alcohol in the step (2), so that the problem that aged particles of the pseudoboehmite are strongly aggregated in strong-polarity water to cause reduction of the pore volume of the pseudoboehmite pore diameter is solved; aging in monohydric alcohol is adopted, and the agglomeration among particles is avoided by reducing the polarity of an aging environment, so that the growth of the particles is facilitated, the crystallinity of the pseudoboehmite is higher, and the crystal is more complete; and (3) copolymerizing a polymer monomer with monohydric alcohol in the pseudo-boehmite, wherein the polymer monomer is used as a bridge bond between the pseudo-boehmite to copolymerize the pseudo-boehmite particles, so that the formed pseudo-boehmite forms a continuous through-channel and has larger aperture and pore volume.
The reaction in the step (2) is a hydrolysis reaction of aluminum monoalcohol carried out.
The preparation method provided by the invention has the advantages of simple process, low production cost and easy operation, and the obtained alumina has the characteristics of high purity, high specific surface, large pore diameter, large pore volume, concentrated pore diameter distribution and through-hole channels.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferred embodiment of the present invention, the monohydric alcohol in step (1) and step (2) is independently C3～C10A monohydric alcohol of (1).
Preferably, the aluminum source of step (1) comprises metallic aluminum.
Preferably, the metallic aluminum comprises any one of aluminum sheet, aluminum ingot or aluminum powder or a combination of at least two of the aluminum sheet, the aluminum ingot or the aluminum powder.
Preferably, the purity of the metal aluminum is more than 99%.
Preferably, in the step (1), the mass ratio of the monohydric alcohol to the aluminum source is 10:1 to 100:1, for example, 10:1, 20:1, 50:1, 75:1, or 100: 1. In the invention, if the monohydric alcohol is too much compared with the aluminum source in the step (1), the loss and unnecessary waste of the aluminum alkoxide solution in the separation process can be caused; if the monohydric alcohol is too small relative to the aluminum source, the aluminum reaction will be incomplete.
Preferably, the initiator I in step (1) comprises any one of aluminum chloride, mercuric chloride or mercuric iodide or a combination of at least two of the two.
As a preferred technical scheme of the invention, the temperature of the reaction in the step (1) is 80-250 ℃, for example, 80 ℃, 100 ℃, 150 ℃, 200 ℃ or 250 ℃.
Preferably, the reaction time in the step (1) is 1-3 h, such as 1h, 1.5h, 2h, 2.5h or 3 h.
Preferably, the pressure of the reaction in step (1) is 0.1 to 10.0MPa, such as 0.1MPa, 1MPa, 2MPa, 5MPa, 8MPa or 10 MPa.
Preferably, the reaction in step (1) is accompanied by stirring, and the stirring speed is 200-1000 r/min.
In the present invention, it is preferable to carry out the operation of step (1) using a reaction vessel equipped with a stirrer, a thermometer, a pressure gauge and a vacuum pump.
Preferably, step (1) further comprises: filtering the solution when the solution is hot after the reaction, and taking the filtrate. In the invention, hot filtration is adopted because the viscosity of the solution can be effectively reduced, and the filtration rate and efficiency are improved.
Preferably, the temperature of the filtration is 80-200 ℃, such as 80 ℃, 100 ℃, 150 ℃ or 200 ℃.
Preferably, the mesh number of the filtering screen is 400-1200 meshes.
In a preferred embodiment of the present invention, the mass ratio of the monoalcohol in step (2) to the monoalcohol aluminum is 100:1 to 2:1, for example, 2:1, 5:1, 10:1, 25:1, 50:1, 75:1, or 100: 1. In the invention, if the monohydric alcohol in the step (2) is too much compared with the monohydric alcohol aluminum, the waste of the subsequent monohydric alcohol separation and the increase of the energy consumption can be caused; if the monohydric alcohol in step (2) is too little compared with the monohydric alcohol aluminum, the aged suspension is sticky and even forms solid viscous liquid, and the aging effect cannot be achieved.
Preferably, the ratio of the mass of the water in the step (2) to the theoretical mass of water required for hydrolysis of the monoalcohol aluminum is 1:1 to 10:1, such as 1:1, 2:1, 5:1, 8:1 or 10:1, and preferably 1:1 to 5: 1. In the present invention, the theoretical water mass required for hydrolysis of the monoalcohol aluminum is the mass of water required theoretically calculated from the reaction equation of the monoalcohol aluminum and water.
Preferably, the molar ratio of water to aluminum monoalcohol in step (2) is 10:1 to 3:1, such as 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, and preferably 5:1 to 3: 1. In the invention, if the mole number of the water in the step (2) is too large relative to that of the monoalcohol aluminum, the pseudo-boehmite particles after the hydrolysis of the monoalcohol aluminum are combined with water to cause the particle particles to be incomplete; if the water in step (2) is present in an amount of too small a molar amount relative to the aluminum monoalcohol, the hydrolysis reaction of the aluminum monoalcohol may be incomplete.
Preferably, the method for mixing and reacting the monohydric alcohol, the aluminum monohydric alcohol solution and the water in the step (2) comprises the following steps: and (2) mixing monohydric alcohol with the monohydric alcohol aluminum solution in the step (1), heating to the reaction temperature, and dropwise adding water while stirring.
Preferably, the reaction temperature is 80 to 100 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃.
Preferably, the time for dripping water is 10-180 min, such as 10min, 25min, 50min, 75min, 100min, 120min, 160min or 180min, and preferably 15-120 min.
As a preferred embodiment of the present invention, the method for removing water in step (2) comprises: vacuum pumping is carried out to remove water.
Preferably, the temperature for aging in step (2) is 100 to 450 ℃, such as 100 ℃, 150 ℃, 200 ℃, 300 ℃, 400 ℃ or 450 ℃, preferably 100 to 200 ℃.
Preferably, the aging time in the step (2) is 1-48 h, such as 1h, 10h, 20h, 30h, 40h or 48h, etc., preferably 1-36 h.
Preferably, the solid-liquid separation of step (2) comprises a filtration separation.
Preferably, the step (2) further comprises drying the solid obtained by the solid-liquid separation.
Preferably, the drying temperature is 100-450 ℃, preferably 100-200 ℃.
Preferably, the drying time is 0.5-3 h.
Preferably, the method of drying comprises flash drying, cyclone drying, oven drying or spray drying.
Preferably, the alcohol content in the pseudo-boehmite containing monohydric alcohol of step (2) is 50 to 90 wt%, such as 50 wt%, 60 wt%, 70 wt%, 80 wt% or 90 wt%, etc., preferably 55 to 85 wt%. In the invention, if the alcohol content in the pseudo-boehmite is too high, excessive alcohol waste can be caused in the subsequent polymerization process, and the separation and energy consumption are improved; if the alcohol content in the pseudo-boehmite is too low, part of the pseudo-boehmite is free from alcohol and polymer monomer, so that the reaction is not uniform.
In a preferred embodiment of the present invention, in the step (3), the mass ratio of the water to the pseudoboehmite containing a monohydric alcohol is 10:1 to 2:1, for example, 2:1, 3:1, 5:1, 8:1, or 10:1, and preferably 5:1 to 2: 1.
Preferably, the initiator II in the step (3) comprises any one of a peroxide initiator, an azo initiator or a redox initiator or a combination of at least two of the two.
Preferably, the peroxide initiator comprises an organic peroxide initiator and/or an inorganic peroxide initiator.
Preferably, the organic peroxide initiator comprises any one of or a combination of at least two of acyl peroxides, hydroperoxides, dialkyl peroxides, ester peroxides, ketone peroxides, or dicarbonate peroxides.
Preferably, the acyl peroxides include benzoyl peroxide and/or lauroyl peroxide.
Preferably, the hydroperoxide comprises cumene hydroperoxide and/or tert-butyl hydroperoxide.
The dialkyl peroxides include di-t-butyl peroxide and/or dicumyl peroxide.
Preferably, the ester peroxide includes t-butyl peroxybenzoate and/or t-butyl peroxypivalate.
Preferably, the ketone peroxide comprises methyl ethyl ketone peroxide and/or cyclohexanone peroxide.
Preferably, the dicarbonate peroxide comprises diisopropyl peroxydicarbonate and/or dicyclohexyl peroxydicarbonate.
Preferably, the inorganic peroxide initiator comprises persulfate initiator, azo initiator, redox initiator, preferably ammonium persulfate and/or potassium persulfate.
Preferably, the persulfate-based initiator comprises any one of potassium persulfate, sodium persulfate, or ammonium persulfate, or a combination of at least two thereof.
Preferably, the azo-type initiator includes azobisisobutyronitrile and/or azobisisoheptonitrile, preferably azobisisobutyronitrile.
Preferably, the redox initiator comprises a combination of benzoyl peroxide and sucrose, a combination of tert-butyl hydroperoxide/rongalite, a combination of tert-butyl hydroperoxide and sodium metabisulfite, a combination of benzoyl peroxide and N, N-dimethylaniline, a combination of ammonium persulfate and sodium bisulfite, a combination of potassium persulfate and sodium bisulfite, a combination of hydrogen peroxide and tartaric acid, a combination of hydrogen peroxide and rongalite, a combination of ammonium persulfate and ferrous sulfate, a combination of hydrogen peroxide and ferrous sulfate, a combination of benzoyl peroxide and N, N-diethylaniline, a combination of benzoyl peroxide and ferrous pyrophosphate, a combination of potassium persulfate and silver nitrate, a combination of persulfate and thiol, a combination of cumene hydroperoxide and ferrous chloride, a combination of potassium persulfate and ferrous chloride, a combination of hydrogen peroxide and ferrous chloride or a combination of cumene hydroperoxide and tetraethenimine, preferably a combination of t-butyl hydroperoxide and sodium metabisulphite.
Preferably, in the step (3), the mass ratio of the polymer monomer to the alcohol in the pseudo-boehmite containing the monohydric alcohol is 5:1 to 1:1, for example, 1:1, 2:1, 3:1, 4:1 or 5: 1. In the present invention, if the amount of the polymer monomer is too much relative to the amount of the alcohol in the pseudo-boehmite containing a monohydric alcohol, it may cause a waste of the polymer monomer; if the amount of the polymer monomer is too small relative to the amount of the alcohol in the alcohol-containing pseudoboehmite, the alcohol-containing pseudoboehmite may not be polymerized.
Preferably, in the step (3), the polymer monomer includes any one of an organic alcohol, an organic acid or an amino acid or a combination of at least two thereof.
Preferably, the organic alcohol comprises a monohydric alcohol and/or a polyhydric alcohol.
Preferably, the monohydric alcohol comprises C6～C10A fatty alcohol.
Preferably, the polyhydric alcohol comprises any one of ethylene glycol, pentaerythritol, 2-propanediol, 1, 4-butanediol, neopentyl glycol, sorbitol, dipropylene glycol, glycerol, xylitol, trimethylolpropane or diethylene glycol, or a combination of at least two thereof.
Preferably, the organic acid comprises any one of tartaric acid, oxalic acid, malic acid, citric acid, acetic acid, succinic acid, ascorbic acid, benzoic acid, salicylic acid or caffeic acid, or a combination of at least two thereof.
Preferably, the amino acid includes any one or a combination of at least two of aspartic acid, glutamic acid, glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine or threonine.
Preferably, the mixing method in step (3) comprises beating mixing.
Preferably, the temperature of the reaction in the step (3) is 100 to 350 ℃, such as 100 ℃, 200 ℃, 300 ℃ or 350 ℃, preferably 150 to 300 ℃.
Preferably, the reaction time in the step (3) is 1.0-48 h, such as 1h, 5h, 10h, 20h, 30h, 40h or 48h, and the like, and preferably 5-36 h.
Preferably, the temperature of the roasting in the step (3) is 300-800 ℃, such as 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃, and the like, and preferably 350-550 ℃.
Preferably, the roasting time in the step (3) is 2.0-5.0 h, such as 2.0h, 3.0h, 4.0h or 5.0h, and the like, and preferably 2.0-4.0 h.
Preferably, step (3) further comprises drying the solid obtained by solid-liquid separation.
Preferably, the drying temperature is 100-450 ℃, preferably 150-400 ℃.
Preferably, the drying time is 1-10 h.
Preferably, the method of drying comprises flash drying, cyclone drying, oven drying or spray drying.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) mixing monohydric alcohol, an aluminum source and an initiator I, and reacting to obtain a monohydric alcohol aluminum solution;
the mass ratio of the monohydric alcohol to the aluminum source is 10: 1-100: 1, the reaction temperature is 80-250 ℃, the reaction time is 1-3 h, the reaction pressure is 0.1-10.0 MPa, stirring is carried out while the reaction is carried out, the stirring speed is 200-1000r/min, the filtrate is obtained by filtering at 80-200 ℃ while the reaction is hot, and the number of the filtered filter screens is 400-1200 meshes;
(2) mixing monohydric alcohol and the monohydric alcohol aluminum solution obtained in the step (1), heating to the reaction temperature of 80-100 ℃, dropwise adding water for 15-120 min while stirring until the water is dropwise added, vacuumizing to evaporate all water, aging in alcohol for 1-36 h at 100-200 ℃, performing solid-liquid separation, and drying to obtain pseudoboehmite containing monohydric alcohol;
wherein the mass ratio of the monohydric alcohol to the monohydric alcohol aluminum solution is 100: 1-2: 1; the mass ratio of the water to the theoretical water mass required for hydrolysis of the monoalcohol aluminum is 1: 1-5: 1; the molar ratio of the water to the monoalcohol aluminum is 5: 1-3: 1; the alcohol content in the pseudo-boehmite containing the monohydric alcohol is 55-85 wt%;
(3) mixing the pseudo-boehmite containing the monohydric alcohol in the step (2) with an initiator II, a polymer monomer and water, heating to 150-300 ℃ for reaction for 5-36 h, performing solid-liquid separation, drying the obtained solid, and roasting at 350-550 ℃ for 2.0-4.0 h to obtain the alumina;
wherein the mass ratio of the water to the pseudo-boehmite containing the monohydric alcohol is 5: 1-2: 1, and the mass ratio of the polymer monomer to the alcohol in the pseudo-boehmite containing the monohydric alcohol is 5: 1-1: 1.
In a second aspect, the present invention provides an alumina obtained by the production method according to the first aspect.
The alumina provided by the invention has the characteristics of high purity, high specific surface, large pore diameter, large pore volume, concentrated pore diameter distribution and through-hole channels.
In a preferred embodiment of the present invention, the alumina has a pore volume of 1.0 to 1.7 mL-g-1For example, 1.0mL · g-1、1.2mL·g-1、1.4mL·g-1、1.5mL·g-1Or 1.7 mL. g-1And the like.
Preferably, the average pore size of the alumina is 25 to 50nm, such as 25nm, 30nm, 35nm, 40nm, 45nm, or 50nm, and the like.
Preferably, the pore size distribution of the alumina is: the proportion of the pore diameter less than 50nm is 0.5-1%, such as 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%; 5-10%, such as 5%, 6%, 7%, 8%, 9% or 10%, etc., and 90-94.5%, such as 90%, 92% or 94.5%, etc., for a pore diameter of greater than 100 nm.
Preferably, the alumina has a particle size distribution such that the proportion of particles with a particle size of less than 1 μm is 5-10%, for example, 5%, 6%, 7%, 8%, 9%, 10%, etc.; 10-30% of 1-10 μm, such as 10%, 15%, 20%, 25% or 30%; the proportion of more than 10 μm is 70-85%, such as 70%, 75%, 80% or 85%.
Preferably, the purity of the alumina is above 99.999%.
In a third aspect, the present invention provides the use of an alumina as described in the second aspect for the preparation of an enhanced treatment catalyst for diesel, wax oil, residual oil, coal tar or coal liquefaction oil.
The alumina provided by the invention is used for the catalyst, can solve the problems of difficult passage of residual oil macromolecular colloid and asphaltene micelle through a pore passage and high diffusion resistance and reaction pressure in the prior art, and slows down the deactivation speed of the catalyst in the heavy oil hydrotreating process.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method provided by the invention, the finally formed pseudoboehmite is aged in the environment of monohydric alcohol through the step (2), so that the problem that the pore volume of the pseudoboehmite is reduced due to strong aggregation of aged particles of the pseudoboehmite in strong polar water is avoided; aging in monohydric alcohol is adopted, and the agglomeration among particles is avoided by reducing the polarity of an aging environment, so that the growth of the particles is facilitated, the crystallinity of the pseudoboehmite is higher, and the crystal is more complete; according to the invention, through the copolymerization of the polymer monomer and monohydric alcohol in the pseudo-boehmite in the step (3), the polymer monomer is used as a bridge bond between the pseudo-boehmite to copolymerize the pseudo-boehmite particles, so that the formed pseudo-boehmite forms a continuous through-channel and has larger aperture and pore volume.
(2) The alumina provided by the invention has the advantages of high purity, high specific surface, large aperture, large pore volume and concentrated aperture distribution, the pore volume is more than 1.01mL/g, the aperture can be more than 11.9nm, and the specific surface area is 406m2The catalyst can solve the problems of difficult passage of residual oil macromolecular colloid and asphaltene micelle through a pore passage, high diffusion resistance and high reaction pressure in the prior art, and slows down the deactivation speed of the catalyst in the heavy oil hydrotreating process.
Drawings
FIG. 1A is an SEM photograph of pseudoboehmite obtained in step (2) in the production method of example 1;
FIG. 1B is an SEM photograph of the pseudoboehmite obtained in step (2) of the production process of example 2;
FIG. 1C is an SEM photograph of the pseudoboehmite obtained in step (2) of the production process of example 3;
FIG. 1D is an SEM photograph of the pseudoboehmite obtained in step (2) of the production process of example 4;
FIG. 1E is an SEM photograph of the pseudoboehmite obtained in step (2) in the production process of comparative example 1;
FIG. 1F is an SEM photograph of the pseudoboehmite obtained in step (2) in the production process of comparative example 2;
FIG. 1G is an SEM photograph of the pseudoboehmite obtained in step (2) in the production process of comparative example 3;
FIG. 2 is an XRD pattern of pseudoboehmite obtained in step (2) in the production processes of examples 1 to 4 and comparative examples 1 to 3, wherein A represents example 1, B represents example 2, C represents example 3, D represents example 4, E represents comparative example 1, F represents comparative example 2, and G represents comparative example 3.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example prepared alumina as follows:
(1) adding 100g of isopropanol, 10g of aluminum powder and 0.1g of aluminum chloride into a high-pressure reaction kettle, starting a stirrer to control the rotating speed to be 500r/min, reacting at the temperature of 95 ℃ and under the pressure of 1.5MPa for 1.5 hours, and filtering by adopting a 1000-mesh filter screen at the temperature of 95 ℃ to obtain an aluminum isopropoxide solution, wherein 110g of aluminum isopropoxide is obtained;
(2) adding the aluminum isopropoxide solution into a high-pressure kettle, adding 500g of isopropanol, heating to the reaction temperature of 95 ℃, then adding 40g of deionized water into the reaction kettle, stirring while dropwise adding, dropwise adding the deionized water in 15min, vacuumizing, evaporating all water, aging at 120 ℃ for 12h, and finally filtering and drying to obtain 80g of pseudo-boehmite containing 75% of isopropanol;
(3) adding the obtained pseudo-boehmite, 1g of benzoyl peroxide, 200g of deionized water and 60g of oxalic acid into the autoclave, uniformly pulping, heating to 200 ℃ for reaction for 24 hours, carrying out solid-liquid separation on the materials after the reaction is finished, drying in a drying oven at 200 ℃ for 5 hours, and roasting at 500 ℃ for 3 hours to obtain the required alumina (marked as A), wherein the properties are listed in Table 1.
An SEM image of the pseudoboehmite obtained by the preparation method provided in this example is shown in fig. 1A, and it can be seen from the figure that the pseudoboehmite mostly presents spherical large particles.
Example 2
This example prepared alumina as follows:
(1) adding 250g of n-hexanol, 20g of aluminum powder and 1.0g of aluminum chloride into a high-pressure reaction kettle, starting a stirrer, controlling the rotating speed to be 1000r/min, reacting at the temperature of 100 ℃ and under the pressure of 2.0MPa for 2 hours, and filtering by adopting a 600-mesh filter screen at the temperature of 100 ℃ to obtain an n-hexanol aluminum solution, wherein 285g of the n-hexanol aluminum is obtained;
(2) adding the solution of the aluminum hexanol into a high-pressure kettle, adding 700g of the hexanol, heating to the reaction temperature of 100 ℃, then adding 100g of deionized water into the reaction kettle, stirring while dropwise adding, dropwise adding the deionized water in 30min, vacuumizing, evaporating all water, aging at 150 ℃ for 36h, and finally filtering and drying to obtain 200g of pseudoboehmite containing 80% of the hexanol;
(3) adding the obtained pseudo-boehmite, 2g of benzoyl peroxide, 600g of deionized water and 100g of xylitol into the autoclave, uniformly pulping, heating to 300 ℃ for reaction for 36 hours, carrying out solid-liquid separation on the materials after the reaction is finished, carrying out spray drying at 300 ℃, and roasting at 450 ℃ for 5 hours to obtain the required alumina (marked as B), wherein the properties are listed in Table 1.
An SEM image of the pseudoboehmite obtained by the preparation method provided in this example is shown in fig. 1B, and it can be seen from the figure that the pseudoboehmite mostly presents spherical large particles.
Example 3
This example prepared alumina as follows:
(1) adding 200g of n-butyl alcohol, 15g of aluminum powder and 1.5g of mercury iodide into a high-pressure reaction kettle, starting a stirrer, controlling the rotating speed to be 1200r/min, reacting at the temperature of 200 ℃ and under the pressure of 5.0MPa for 1 hour, and filtering by using a 1200-mesh filter screen at the temperature of 150 ℃ to obtain an n-butyl aluminum alkoxide solution, wherein the n-butyl aluminum alkoxide is 220 g;
(2) adding the n-butanol aluminum solution into a high-pressure kettle, adding 500g of n-butanol, heating to the reaction temperature of 95 ℃, then adding 150g of deionized water into the reaction kettle, stirring while dropwise adding, completely dropwise adding the deionized water within 60min, vacuumizing to completely evaporate water, aging at 200 ℃ for 24h, and finally filtering and drying to obtain 180g of pseudoboehmite containing 85% of n-butanol;
(3) adding the obtained pseudo-boehmite, 3g of benzoyl peroxide, 900g of deionized water and 120g of glutamic acid into the autoclave, pulping uniformly, heating to 250 ℃ for reaction for 12 hours, carrying out solid-liquid separation on the materials after the reaction is finished, carrying out cyclone drying at 300 ℃, and roasting at 550 ℃ for 4 hours to obtain the required alumina (marked as C), wherein the properties are listed in Table 1.
An SEM image of the pseudoboehmite obtained by the preparation method provided in this example is shown in fig. 1C, and it can be seen from the SEM image that the pseudoboehmite mostly presents large spherical particles.
Example 4
This example prepared alumina as follows:
(1) adding 400g of n-octanol, 50g of aluminum powder and 2.0g of mercuric chloride into a high-pressure reaction kettle, starting a stirrer to control the rotating speed to be 800r/min, reacting at the temperature of 250 ℃ and under the pressure of 10.0MPa for 3 hours, and filtering by adopting a 1000-mesh filter screen at the temperature of 200 ℃ to obtain an n-octanol aluminum solution, wherein 425g of n-hexanol aluminum is obtained;
(2) adding the n-octanol aluminum solution into a high-pressure kettle, adding 800g of n-octanol, heating to the reaction temperature of 95 ℃, then adding 200g of deionized water into the reaction kettle, stirring while dropwise adding, dropwise adding the deionized water in 90min, vacuumizing to completely evaporate water, aging at 180 ℃ for 36h, and finally filtering and drying to obtain 350g of pseudo-boehmite containing 75% of n-butanol;
(3) adding the obtained pseudo-boehmite, 5g of benzoyl peroxide, 800g of deionized water and 270g of glutamic acid into the autoclave, pulping uniformly, heating to 250 ℃ for reaction for 8 hours, carrying out solid-liquid separation on the materials after the reaction is finished, carrying out cyclone drying at 350 ℃, and roasting at 500 ℃ for 5 hours to obtain the required alumina (marked as D), wherein the properties are listed in Table 1.
An SEM image of the pseudoboehmite obtained by the preparation method provided in this example is shown in fig. 1D, and it can be seen from the SEM image that the pseudoboehmite mostly presents spherical large particles.
Comparative example 1
This comparative example prepared alumina as follows:
(1) adding 200g of isopropanol, 15g of aluminum powder and 0.2g of aluminum chloride into a high-pressure reaction kettle, starting a stirrer to control the rotating speed to be 800r/min, reacting at the temperature of 100 ℃ and under the pressure of 2.0MPa for 2 hours, and filtering by adopting a 1100-mesh filter screen at the temperature of 100 ℃ to obtain an aluminum isopropoxide solution, wherein 220g of aluminum n-hexanoate is obtained;
(2) adding the aluminum isopropoxide solution into an autoclave, adding 600g of isopropanol, heating to the reaction temperature of 100 ℃, adding 50g of deionized water into the autoclave while stirring, dropwise adding the deionized water in 15min, vacuumizing to evaporate all water, aging at 120 ℃ for 12h, performing solid-liquid separation on the aged material, drying in a drying oven at 200 ℃ for 5h to obtain pseudoboehmite, and roasting at 500 ℃ for 3h to obtain the required aluminum oxide (marked as E), wherein the properties are listed in Table 1.
The SEM image of the pseudoboehmite obtained by the preparation method provided by the comparison is shown in FIG. 1E, and it can be seen from the SEM image that the pseudoboehmite mostly presents spherical small particles.
Comparative example 2
This comparative example prepared alumina as follows:
(1) adding 300g of n-butyl alcohol, 25g of aluminum powder and 2.0g of mercury iodide into a high-pressure reaction kettle, starting a stirrer, controlling the rotating speed to be 1000r/min, reacting at the temperature of 180 ℃ and under the pressure of 8.0MPa for 2 hours, and filtering by using a 1200-mesh filter screen at the temperature of 150 ℃ to obtain an n-butyl aluminum alkoxide solution, wherein the n-butyl aluminum alkoxide is 330 g;
(2) adding the n-butanol aluminum solution into an autoclave, adding 500g of n-butanol, heating to the reaction temperature of 95 ℃, then adding 150g of deionized water into the autoclave while stirring, adding 900g of deionized water into the autoclave after dropwise adding the deionized water for 60min, aging the obtained filter cake in the autoclave at 200 ℃ for 24h, carrying out solid-liquid separation on the aged material, carrying out cyclone drying at 300 ℃ to obtain pseudo-boehmite, and roasting at 550 ℃ for 4h to obtain the required aluminum oxide (marked as F), wherein the properties are listed in Table 1.
The SEM image of the pseudoboehmite obtained by the preparation method provided by the comparison is shown in FIG. 1F, and it can be seen from the SEM image that the pseudoboehmite mostly presents spherical small particles.
Comparative example 3
This comparative example prepared alumina as follows:
(1) adding 200g of n-hexanol, 20g of aluminum powder and 1.1g of aluminum chloride into a high-pressure reaction kettle, starting a stirrer to control the rotating speed to be 1200r/min, reacting at the temperature of 95 ℃ and under the pressure of 2.0MPa for 1.5 hours, and filtering at the temperature of 95 ℃ by using a 800-mesh filter screen to obtain an n-hexanol aluminum solution, wherein the amount of the n-hexanol aluminum is 220 g;
(2) adding the aluminum hexanol solution into a high-pressure kettle, adding 700g of hexanol, heating to the reaction temperature of 100 ℃, then adding 100g of deionized water into the reaction kettle, stirring while dropwise adding, dropwise adding the deionized water in 30min, adding the filtered filter cake and 600g of water into the high-pressure kettle, aging at 150 ℃ for 36h, and finally filtering to obtain 200g of pseudoboehmite;
(3) adding the obtained pseudo-boehmite, 2G of benzoyl peroxide, 600G of deionized water and 100G of xylitol into the autoclave, pulping uniformly, heating to 300 ℃ for reaction for 36 hours, carrying out solid-liquid separation on the materials after the reaction is finished, carrying out spray drying at 300 ℃, and roasting at 450 ℃ for 5 hours to obtain the required alumina (marked as G), wherein the properties are listed in Table 1.
The SEM image of the pseudoboehmite obtained by the preparation method provided by the comparison is shown in FIG. 1G, and it can be seen from the SEM image that the pseudoboehmite mostly presents spherical small particles.
Comparative example 4
This comparative example prepared alumina as follows:
(1) putting 150g of waste electronic aluminum foil with the purity of 99.99% and the thickness of 3mm and 1000g of isopropanol into a 5L reactor, reacting for 7h at 83 ℃ under the catalysis of mercuric chloride to obtain aluminum isopropoxide alkoxide, and preserving heat for 10h at 180 ℃;
(2) transferring the substance obtained in the step (1) after heat preservation into a 3L container, distilling and purifying for 10h at 180 ℃, removing waste residues to obtain purified isopropanol aluminum alkoxide, transferring the purified isopropanol aluminum alkoxide into a hydrolysis reaction kettle, adding nano-diaspore seed crystals (diaspore raw powder with the crystallinity of 78 percent and the grain size of 30 nm) with the mass of 5 per thousand of the isopropanol aluminum alkoxide, adding an alcohol solution according to the molar ratio of 1:22, mixing (the alcohol solution is obtained by mixing deionized water and isopropanol according to the molar ratio of 1: 6), and then preserving heat for 7.5h at 155 ℃;
(3) and (3) mechanically stirring and hydrolyzing the substance obtained after heat preservation in the step (2) at 75 ℃ for 8H, adding an auxiliary agent citric acid with the mass of 0.5% of the substance obtained after hydrolysis into a mixed solution of alcohol and deionized water with the alcohol content of 70%, preserving the heat at 165 ℃ for 9H, finally spray-drying at 300 ℃, and roasting at 450 ℃ for 5H to obtain the required aluminum oxide (marked as H), wherein the properties of the aluminum oxide are listed in Table 1.
Comparative example 5
Referring to example 1, the alumina preparation method of the present comparative example is different in that after the deionized water is added in step (2) of the present comparative example, the filtration is performed to obtain a filter cake, 900g of deionized water is added to the filter cake, and the filter cake is placed in an autoclave and aged in water.
The properties of the alumina obtained in this comparative example are shown in Table 2.
Comparative example 6
The alumina production process of this comparative example is referred to example 1 except that the operation of step (3) of this comparative example is: and (3) performing solid-liquid separation on the pseudo-boehmite containing 75% of isopropanol in the step (2) to obtain a solid, drying the solid in a drying oven at 200 ℃ for 5 hours, and roasting the dried solid at 500 ℃ for 3 hours to obtain the required alumina.
The properties of the alumina obtained in this comparative example are shown in Table 2.
Test method
XRD test was performed on the pseudo-boehmite provided in examples 1 to 4 and comparative examples 1 to 3 by using an XRD diffractometer, and the test results are shown in FIG. 2. The width of the XRD diffraction peak of the pseudo-boehmite in the figure is narrower and sharp, and the peak intensity is higher, so that the pseudo-boehmite provided by the embodiments 1-4 has higher crystallinity and purity.
The specific surface area, pore size, pore volume and pore size distribution of the alumina provided in each example and comparative example were measured by low temperature liquid nitrogen adsorption.
The particle size distributions of the aluminas provided in the examples and comparative examples were determined using a laser particle size distribution instrument.
The test results are shown in the following table:
TABLE 1
TABLE 2
As can be seen from the data in tables 1 and 2, the alumina prepared in examples 1-4 has large specific surface area, large pore diameter and large pore volume, and the distribution of the pore diameters is mainly several in the range of more than 100nm, so that more diffusion channels can be provided for macromolecules in heavy oil hydrotreating; the particle size is larger and the particle size distribution is more concentrated.
Comparative example 1 mainly because polymerization was carried out without addition of a polymerization monomer, a space network structure could not be formed between pseudo-boehmite particles, and pore volume of pore diameter was small.
Comparative example 2 mainly because of aging in water and subsequent polymerization without addition of a polymerizable monomer, irregular aggregation of particles was caused in strongly polar water, and the particles could not form a spatial network structure without polymerization, and the pore volume of the pore diameter was small.
Comparative example 3 caused irregular aggregation of particles in strongly polar water mainly due to aging in water.
Comparative example 4 is a preparation method of the prior art, which causes irregular aggregation of particles in strong polar water due to aging in water and subsequent polymerization without addition of a polymerization monomer, and causes no formation of a spatial network structure of particles by polymerization, and has a small pore volume of pore diameter.
Comparative example 5 resulted in irregular aggregation of particles in strongly polar water due to aging in water.
Comparative example 6 No polymerized monomer was added for polymerization, so that a space network structure could not be formed between pseudo-boehmite particles and the pore volume of the pore diameter was small.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (77)
1. A method for preparing alumina, characterized in that the method comprises the following steps:
(1) mixing monohydric alcohol, an aluminum source and an initiator I, and reacting to obtain a monohydric alcohol aluminum solution;
(2) mixing monohydric alcohol, the monohydric alcohol aluminum solution obtained in the step (1) and water for reaction, removing water, aging in alcohol, and carrying out solid-liquid separation to obtain pseudo-boehmite containing monohydric alcohol;
(3) and (3) mixing the pseudo-boehmite containing the monohydric alcohol in the step (2) with an initiator II, a polymer monomer and water, heating for reaction, carrying out solid-liquid separation, and roasting the obtained solid to obtain the alumina.
2. The method according to claim 1, wherein the monohydric alcohol in step (1) and step (2) is independently C3～C10A monohydric alcohol of (1).
3. The method of claim 1, wherein the aluminum source of step (1) comprises aluminum metal.
4. The method according to claim 3, wherein the metallic aluminum comprises any one of aluminum flakes, aluminum ingots, or aluminum flakes, or a combination of at least two thereof.
5. The method according to claim 3, wherein the purity of the metallic aluminum is 99% or more.
6. The method according to claim 1, wherein in the step (1), the mass ratio of the monohydric alcohol to the aluminum source is 10:1 to 100: 1.
7. The preparation method according to claim 1, wherein the initiator I in the step (1) comprises any one of aluminum chloride, mercuric chloride or mercuric iodide or a combination of at least two of the above.
8. The method according to claim 1, wherein the temperature of the reaction in the step (1) is 80 to 250 ℃.
9. The preparation method according to claim 1, wherein the reaction time in the step (1) is 1-3 h.
10. The method according to claim 1, wherein the pressure of the reaction in the step (1) is 0.1 to 10.0 MPa.
11. The method as claimed in claim 1, wherein the reaction in step (1) is accompanied by stirring at a speed of 200-1000 r/min.
12. The method of claim 1, wherein step (1) further comprises: filtering the solution when the solution is hot after the reaction, and taking the filtrate.
13. The method according to claim 12, wherein the temperature of the filtration is 80 to 200 ℃.
14. The method according to claim 12, wherein the filtering mesh number is 400-1200 mesh.
15. The preparation method according to claim 1, wherein the mass ratio of the monohydric alcohol to the aluminum monohydric alcohol in the step (2) is 100:1 to 2: 1.
16. The preparation method according to claim 1, wherein the ratio of the mass of the water in the step (2) to the theoretical mass of the water required for hydrolysis of the monoalcohol aluminum is 1:1 to 10: 1.
17. The preparation method according to claim 16, wherein the ratio of the mass of the water in the step (2) to the theoretical mass of the water required for hydrolysis of the monoalcohol aluminum is 1:1 to 5: 1.
18. The preparation method according to claim 1, wherein the molar ratio of the water to the aluminum monoalcohol in step (2) is 10:1 to 3: 1.
19. The preparation method according to claim 18, wherein the molar ratio of the water to the aluminum monoalcohol in step (2) is 5:1 to 3: 1.
20. The method according to claim 1, wherein the step (2) of mixing and reacting the monohydric alcohol, the aluminum monoalcohol solution of step (1), and water comprises: and (2) mixing monohydric alcohol with the monohydric alcohol aluminum solution in the step (1), heating to the reaction temperature, and dropwise adding water while stirring.
21. The method according to claim 20, wherein the reaction temperature is 80 to 100 ℃.
22. The method according to claim 20, wherein the time for dropping water is 10 to 180 min.
23. The method according to claim 22, wherein the time for dripping water is 15 to 120 min.
24. The method of claim 1, wherein the method of removing water in step (2) comprises: vacuum pumping is carried out to remove water.
25. The method according to claim 1, wherein the aging temperature in the step (2) is 100 to 450 ℃.
26. The method according to claim 25, wherein the aging temperature in the step (2) is 100 to 200 ℃.
27. The preparation method according to claim 1, wherein the aging time in the step (2) is 1-48 h.
28. The preparation method of claim 27, wherein the aging time in the step (2) is 1-36 h.
29. The production method according to claim 1, wherein the solid-liquid separation of step (2) comprises filtration separation.
30. The method according to claim 1, wherein the step (2) further comprises drying the solid obtained by the solid-liquid separation.
31. The method according to claim 30, wherein the drying temperature is 100 to 450 ℃.
32. The method according to claim 31, wherein the drying temperature is 100 to 200 ℃.
33. The method according to claim 30, wherein the drying time is 0.5 to 3 hours.
34. The method of claim 30, wherein the drying comprises flash drying, cyclone drying, oven drying, or spray drying.
35. The method according to claim 1, wherein the alcohol content in the monoalcohol-containing pseudoboehmite in step (2) is 50 to 90 wt%.
36. The method according to claim 35, wherein the alcohol content in the boehmite containing a monohydric alcohol in the step (2) is 55 to 85 wt%.
37. The method according to claim 1, wherein in the step (3), the mass ratio of the water to the pseudoboehmite containing the monohydric alcohol is 10:1 to 2: 1.
38. The method according to claim 37, wherein in the step (3), the mass ratio of the water to the pseudoboehmite containing the monohydric alcohol is 5:1 to 2: 1.
39. The method according to claim 1, wherein the initiator II in the step (3) comprises any one of a peroxide initiator, an azo initiator or a redox initiator or a combination of at least two of them.
40. A method as claimed in claim 39, wherein the peroxide initiator comprises an organic peroxide initiator and/or an inorganic peroxide initiator.
41. The method of claim 40, wherein the organic peroxide initiator comprises any one of or a combination of at least two of acyl peroxides, hydroperoxides, dialkyl peroxides, ester peroxides, ketone peroxides, or dicarbonate peroxides.
42. The method according to claim 41, wherein the acyl peroxide comprises benzoyl peroxide and/or lauroyl peroxide.
43. A method as claimed in claim 41, wherein said hydroperoxide comprises cumene hydroperoxide and/or tert-butyl hydroperoxide.
44. The method of claim 41, wherein the dialkyl peroxide comprises di-t-butyl peroxide and/or dicumyl peroxide.
45. The method as claimed in claim 41, wherein the ester peroxide comprises t-butyl peroxybenzoate and/or t-butyl peroxypivalate.
46. The method according to claim 41, wherein the ketone peroxide comprises methyl ethyl ketone peroxide and/or cyclohexanone peroxide.
47. The method of claim 41, wherein the dicarbonate peroxide comprises diisopropyl peroxydicarbonate and/or dicyclohexyl peroxydicarbonate.
48. The method of claim 40, wherein the inorganic peroxide initiator comprises persulfate initiators, azo initiators, and redox initiators.
49. A method as claimed in claim 48, wherein said persulfate type initiator comprises any one or a combination of at least two of potassium persulfate, sodium persulfate, or ammonium persulfate.
50. The method according to claim 48, wherein the azo initiator comprises azobisisobutyronitrile and/or azobisisoheptonitrile.
51. The method of claim 48, wherein said redox initiator comprises a combination of benzoyl peroxide and sucrose, a combination of t-butyl hydroperoxide/rongalite, a combination of t-butyl hydroperoxide and sodium metabisulfite, a combination of benzoyl peroxide and N, N-dimethylaniline, a combination of ammonium persulfate and sodium bisulfite, a combination of potassium persulfate and sodium bisulfite, a combination of hydrogen peroxide and tartaric acid, a combination of hydrogen peroxide and rongalite, a combination of ammonium persulfate and ferrous sulfate, a combination of hydrogen peroxide and ferrous sulfate, a combination of benzoyl peroxide and N, N-diethylaniline, a combination of benzoyl peroxide and ferrous pyrophosphate, a combination of potassium persulfate and silver nitrate, a combination of persulfate and thiol, a combination of cumene hydroperoxide and ferrous chloride, A combination of potassium persulfate and ferrous chloride, a combination of hydrogen peroxide and ferrous chloride, or a combination of cumene hydroperoxide and tetraethylene imine;
52. the method according to claim 1, wherein in the step (3), the mass ratio of the polymer monomer to the alcohol in the boehmite containing the monohydric alcohol is 5:1 to 1: 1.
53. The method according to claim 1, wherein in the step (3), the polymer monomer comprises any one of an organic alcohol, an organic acid, or an amino acid, or a combination of at least two thereof.
54. The method of claim 53, wherein the organic alcohol comprises a monohydric alcohol and/or a polyhydric alcohol.
55. A method of making as set forth in claim 54, wherein the monohydric alcohol comprises C6～C10A fatty alcohol.
56. The method of claim 54, wherein the polyol comprises any one of ethylene glycol, pentaerythritol, 2-propanediol, 1, 4-butanediol, neopentyl glycol, sorbitol, dipropylene glycol, glycerol, xylitol, trimethylolpropane, or diethylene glycol, or a combination of at least two thereof.
57. The method of claim 53, wherein the organic acid comprises one or a combination of at least two of tartaric acid, oxalic acid, malic acid, citric acid, acetic acid, succinic acid, ascorbic acid, benzoic acid, salicylic acid, and caffeic acid.
58. The method according to claim 53, wherein the amino acid comprises any one or a combination of at least two of aspartic acid, glutamic acid, glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine, and threonine.
59. The method of claim 1, wherein the mixing in step (3) comprises beating mixing.
60. The method according to claim 1, wherein the temperature of the reaction in the step (3) is 100 to 350 ℃.
61. The method according to claim 60, wherein the temperature of the reaction in the step (3) is 150 to 300 ℃.
62. The preparation method according to claim 1, wherein the reaction time in the step (3) is 1.0-48 h.
63. The preparation method according to claim 62, wherein the reaction time in the step (3) is 5-36 h.
64. The method according to claim 1, wherein the temperature of the calcination in the step (3) is 300 to 800 ℃.
65. The preparation method of claim 64, wherein the roasting temperature in the step (3) is 350-550 ℃.
66. The preparation method of claim 1, wherein the roasting time in the step (3) is 2.0-5.0 h.
67. The preparation method of claim 66, wherein the roasting time in the step (3) is 2.0-4.0 h.
68. The method according to claim 1, wherein the step (3) further comprises drying the solid obtained by the solid-liquid separation.
69. The method as claimed in claim 68, wherein the drying temperature is 100-450 ℃.
70. The method as claimed in claim 69, wherein the drying temperature is 150-400 ℃.
71. The method as claimed in claim 68, wherein the drying time is 1-10 h.
72. The method of claim 68, wherein the drying comprises flash drying, cyclone drying, oven drying, or spray drying.
73. The method for preparing according to claim 1, characterized in that it comprises the following steps:
(1) mixing monohydric alcohol, an aluminum source and an initiator I, and reacting to obtain a monohydric alcohol aluminum solution;
the mass ratio of the monohydric alcohol to the aluminum source is 10: 1-100: 1, the reaction temperature is 80-250 ℃, the reaction time is 1-3 h, the reaction pressure is 0.1-10.0 MPa, stirring is carried out while the reaction is carried out, the stirring speed is 200-1000r/min, the filtrate is obtained by filtering at 80-200 ℃ while the reaction is hot, and the number of the filtered filter screens is 400-1200 meshes;
(2) mixing monohydric alcohol and the monohydric alcohol aluminum solution obtained in the step (1), heating to the reaction temperature of 80-100 ℃, dropwise adding water for 15-120 min while stirring until the water is dropwise added, vacuumizing to evaporate all water, aging in alcohol for 1-36 h at 100-200 ℃, performing solid-liquid separation, and drying to obtain pseudoboehmite containing monohydric alcohol;
wherein the mass ratio of the monohydric alcohol to the monohydric alcohol aluminum solution is 100: 1-2: 1; the mass ratio of the water to the theoretical water mass required for hydrolysis of the monoalcohol aluminum is 1: 1-5: 1; the molar ratio of the water to the monoalcohol aluminum is 5: 1-3: 1; the alcohol content in the pseudo-boehmite containing the monohydric alcohol is 55-85 wt%;
(3) mixing the pseudo-boehmite containing the monohydric alcohol in the step (2) with an initiator II, a polymer monomer and water, heating to 150-300 ℃ for reaction for 5-36 h, performing solid-liquid separation, drying the obtained solid, and roasting at 350-550 ℃ for 2.0-4.0 h to obtain the alumina;
wherein the mass ratio of the water to the pseudo-boehmite containing the monohydric alcohol is 5: 1-2: 1, and the mass ratio of the polymer monomer to the alcohol in the pseudo-boehmite containing the monohydric alcohol is 5: 1-1: 1.
74. Alumina obtained by the method of any one of claims 1 to 73, having a pore size distribution of: the proportion of the aperture less than 50nm is 0.5-1%, the proportion of the aperture 50-100 nm is 5-10%, and the proportion of the aperture more than 100nm is 90-94.5%.
75. The alumina of claim 74, wherein the alumina has a pore volume of 1.0 to 1.7 mL-g-1。
76. The alumina of claim 74, wherein the alumina has a particle size distribution such that the proportion of particles having a particle size of less than 1 μm is 5 to 10%, the proportion of particles having a particle size of 1 to 10 μm is 10 to 30%, and the proportion of particles having a particle size of more than 10 μm is 70 to 85%.
77. Use of the alumina according to any one of claims 74 to 76 as an enhanced treatment catalyst for the production of diesel, wax oil, residual oil, coal tar or coal liquefaction oil.
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