CN117839676A - Metal composite oxide and preparation method and application thereof - Google Patents
Metal composite oxide and preparation method and application thereof Download PDFInfo
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- CN117839676A CN117839676A CN202410000274.4A CN202410000274A CN117839676A CN 117839676 A CN117839676 A CN 117839676A CN 202410000274 A CN202410000274 A CN 202410000274A CN 117839676 A CN117839676 A CN 117839676A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 73
- 239000011148 porous material Substances 0.000 claims abstract description 63
- 239000000084 colloidal system Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 230000032683 aging Effects 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 238000000227 grinding Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 53
- 229910052684 Cerium Inorganic materials 0.000 claims description 46
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 38
- 150000000703 Cerium Chemical class 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 33
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 31
- 150000004645 aluminates Chemical class 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000012530 fluid Substances 0.000 claims description 14
- 238000003801 milling Methods 0.000 claims description 12
- 150000007529 inorganic bases Chemical class 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 7
- 244000205754 Colocasia esculenta Species 0.000 claims description 6
- 235000006481 Colocasia esculenta Nutrition 0.000 claims description 6
- 239000000295 fuel oil Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- -1 Ce (NO 3 ) 3 ·6H 2 O Chemical class 0.000 claims description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 44
- 229910021641 deionized water Inorganic materials 0.000 description 44
- 239000002244 precipitate Substances 0.000 description 26
- 238000001035 drying Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
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- 230000000052 comparative effect Effects 0.000 description 13
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 11
- 238000010304 firing Methods 0.000 description 11
- 238000000643 oven drying Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
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- 238000000975 co-precipitation Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
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- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JHKXZYLNVJRAAJ-WDSKDSINSA-N Met-Ala Chemical compound CSCC[C@H](N)C(=O)N[C@@H](C)C(O)=O JHKXZYLNVJRAAJ-WDSKDSINSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Abstract
The invention provides a metal composite oxide and a preparation method and application thereof, belonging to the technical field of catalyst preparation. The metal composite oxide provided by the invention is prepared from CeO 2 And gamma-Al 2 O 3 Composition; the CeO 2 Loaded on gamma-Al 2 O 3 Is a surface of (2); the CeO 2 With gamma-Al 2 O 3 The mass ratio of (2) is 1:9-3:7; the specific surface area of the metal composite oxide is more than or equal to 380m 2 Per gram, pore volume is more than or equal to 1.4cm 3 And/g, the pore diameter is more than or equal to 14nm. The invention improves the specific surface area, pore volume and pore diameter of the metal composite oxide by a plurality of technical means of colloid mill, pH value adjustment, gel reaction, aging and roasting, thereby improving the catalytic activity of the metal composite oxide as a catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a metal composite oxide, a preparation method and application thereof.
Background
Alumina Al 2 O 3 Is a high-hardness inorganic compound, wherein gamma-Al 2 O 3 Is a widely applied catalyst carrier, has acidic surface, and has the characteristics of stable chemical property, low cost and the like. However, with the rapid development of industrial technology, the gamma Al prepared by the prior art 2 O 3 The specific surface area, pore volume and pore diameter of (a) have not been satisfactory for production.
CeO 2 Is rare earth metal oxide with rich reserves and CeO 2 Is nontoxic, has a unique 4f electronic structure and has wide application in the field of catalysts.
Chinese patent publication No. CN103433018A discloses a CeO 2 /γ-Al 2 O 3 Preparation method of multi-stage structure composite microsphere, ceO prepared by the patent 2 /γ-Al 2 O 3 Is a hollow microsphere constructed by nano-thin sheets, and the CeO sample is not represented in the patent 2 /γ-Al 2 O 3 Is a specific surface area, pore volume and pore diameter. Song Xiaolan et al (Song Xiaolan, wu Xuelan, et al, co-precipitation method for synthesizing CeO) 2 /γ-Al 2 O 3 Study of composite nanocrystalline, rare earth, 12 months of 2004, 25 th volume, 6 th phase, pages 10-14) discloses the preparation of CeO by chemical coprecipitation method 2 /γ-Al 2 O 3 Composite nanocrystalline powder to prepare CeO 2 /γ-Al 2 O 3 The specific surface area of the composite nanocrystalline powder is only 199.58m 2 And/g. CeO obtained by the above preparation methods 2 /γ-Al 2 O 3 The surface area of the product is generally less than 300m 2 Per gram, pore volume of not more than 1.1cm 3 The pore diameter is smaller than 12nm, and the problems of small specific surface area, pore volume and pore diameter are present.
Disclosure of Invention
In view of the above, the present invention is directed to a metal composite oxide, and a preparation method and application thereof. The metal composite oxide provided by the invention has the advantages of large specific surface area, large pore volume and large pore diameter.
In order to achieve the above object, the present invention provides the following technical solutions:
metalA composite oxide of CeO 2 And gamma-Al 2 O 3 Composition; the CeO 2 Loaded on the gamma-Al 2 O 3 Is a surface of (2); the CeO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 1:9-3:7;
the specific surface area of the metal composite oxide is more than or equal to 380m 2 Per gram, pore volume is more than or equal to 1.4cm 3 And/g, the pore diameter is more than or equal to 14nm.
Preferably, the metal composite oxide is prepared from the preparation raw materials through colloid milling, pH value adjustment, gel reaction, aging and roasting; the preparation raw materials comprise aluminum salt, aluminate and cerium-containing compound.
The invention provides a preparation method of the metal composite oxide, which comprises the following steps:
mixing aluminum salt, a cerium-containing compound and water to obtain a mixed solution A;
colloid milling is carried out on the mixed solution A and the aluminate solution to obtain grinding solution A;
adjusting the pH value of the grinding fluid A to be alkaline, and performing a gel reaction to obtain a gel system A;
aging the gel system A to obtain cerium-containing pseudo-boehmite A;
and roasting the cerium-containing pseudo-boehmite A to obtain the metal composite oxide.
Preferably, the aluminum salt is Al 2 (SO 4 ) 3 ·18H 2 O、AlCl 3 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 One or more of O; the aluminate is NaAlO 2 And KAlO 2 One or two of the following components; the cerium-containing compound is cerium salt and CeO 2 One or both of the cerium salts including Ce (NO 3 ) 3 ·6H 2 O、CeCl 3 ·7H 2 O、Ce 2 (SO 4 ) 3 ·8H 2 O and (NH) 4 ) 2 Ce(NO 3 ) 6 One or more of the following.
Preferably, in the grinding liquid A, the molar ratio of the aluminum salt to the aluminate to the cerium-containing compound is 1:2-6:0.01-0.04;
the rotating speed of the colloid mill is 1000-3000 r/min, the temperature is 20-25 ℃ and the time is 5-10 min;
the pH value range is 7.92-9.68;
the temperature of the gel reaction is 25-75 ℃, the time is 1-5 h, and the stirring speed is 100-600 r/min;
the aging temperature is 25-75 ℃ and the aging time is 1-5 h;
the temperature of the gel reaction is less than the aging temperature;
the roasting temperature is 400-600 ℃, and the roasting time is 2-4 h.
Preferably, the CeO 2 The preparation method of the (C) comprises the following steps:
mixing cerium salt, water and inorganic base, and performing precipitation reaction to obtain Ce (OH) 3 ；
The Ce (OH) 3 First roasting to obtain CeO 2 。
The inorganic base comprises NaOH, KOH and Ca (OH) 2 One or more of the following; OH in the cerium salt and inorganic base - The molar ratio of (2) is 1:3-6;
the temperature of the first roasting is 400-600 ℃ and the time is 2-4 h.
The invention also provides another preparation method of the metal composite oxide, which comprises the following steps:
colloid milling is carried out on the aluminum salt solution and the aluminate solution to obtain grinding liquid B;
adjusting the pH value of the grinding fluid B to be alkaline, and performing a gel reaction to obtain a gel system B;
aging the gel system B to obtain pseudo-boehmite B;
the pseudo-boehmite B is subjected to first roasting to obtain gamma-Al 2 O 3 ；
Subjecting the gamma-Al to 2 O 3 Grinding and mixing cerium salt and water, and performing second roasting to obtain the metal composite oxide.
Preferably, the aluminum salt is Al 2 (SO 4 ) 3 ·18H 2 O、AlCl 3 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 One or more of O; the aluminate is NaAlO 2 And KAlO 2 One or two of the following components; the cerium salt includes Ce (NO) 3 ) 3 ·6H 2 O、CeCl 3 ·7H 2 O、Ce 2 (SO 4 ) 3 ·8H 2 O and (NH) 4 ) 2 Ce(NO 3 ) 6 One or more of the following.
Preferably, in the grinding liquid B, the molar ratio of the aluminum salt to the aluminate is 1:2-6;
the rotating speed of the colloid mill is 1000-3000 r/min, the temperature is 20-25 ℃ and the time is 5-10 min;
the pH value range is 7.92-9.68;
the temperature of the gel reaction is 25-75 ℃, the time is 1-5 h, and the stirring speed is 100-600 r/min;
the aging temperature is 25-75 ℃ and the aging time is 1-5 h;
the temperature of the gel reaction is less than the aging temperature;
the temperature of the first roasting is 400-600 ℃ and the time is 2-4 h;
the gamma-Al 2 O 3 The ratio of the water to the water is 1g (1.4-1.6) mL; the gamma-Al 2 O 3 And cerium salt in the molar ratio of 40:1-4;
the temperature of the second roasting is 400-600 ℃ and the time is 2-4 h.
The invention provides the application of the metal composite oxide as the catalyst in heavy oil catalytic cracking.
The present invention provides a metal composite oxide comprising CeO 2 And gamma-Al 2 O 3 Composition; the CeO 2 Loaded on gamma-Al 2 O 3 Is a surface of (2); the CeO 2 With gamma-Al 2 O 3 The mass ratio of (2) is 1:9-3:7; the specific surface area of the metal composite oxide is more than or equal to 380m 2 Per gram, pore volume is more than or equal to 1.4cm 3 /g, pore sizeAnd the wavelength is more than or equal to 14nm. The metal composite oxide provided by the invention contains CeO with specific mass ratio 2 With gamma-Al 2 O 3 ，CeO 2 Loaded to gamma-Al 2 O 3 Surface-modified CeO of the whole metal composite oxide 2 -γAl 2 O 3 The metal composite oxide provided by the invention has the advantages of large specific surface area, large pore volume and large pore diameter at the same time, thereby improving the catalytic activity of the metal composite oxide as a catalyst.
The invention provides two preparation methods of the metal composite oxide, wherein the first preparation method is to directly mix and react aluminum salt, aluminate and cerium-containing compound to obtain the metal composite oxide, the preparation method can regulate and control the mixing degree of the aluminum salt, aluminate and cerium-containing compound, the prepared catalyst is uniformly mixed, and the active center CeO is an active center 2 In gamma-Al 2 O 3 The dispersity of the surface is good, and the particle size of the prepared metal composite oxide is moderate. The second preparation method is to prepare gamma-Al first 2 O 3 Then, gamma-Al is added 2 O 3 And cerium salt to obtain the metal composite oxide by mixing and roasting, the preparation method has the advantages that: the method has the advantages of simple operation and strong controllability, can omit the operation of filtering redundant solution in the actual preparation process, is convenient for controlling the content of the active component cerium salt in the catalyst, and is beneficial to saving the consumption of the cerium salt. By directly combining cerium salt with gamma-Al 2 O 3 Mixing and roasting to obtain CeO 2 Most of them are distributed in gamma-Al 2 O 3 The utilization rate of the cerium salt as an active component is improved.
The invention provides a preparation method of the metal composite oxide, which comprises the steps of adopting aluminum salt, aluminate and cerium-containing compound, colloid milling, adjusting pH value, performing gel reaction, aging and roasting to obtain the metal composite oxide. The invention makes the mixed material produce strong shearing, molecular friction and turbulence through the colloid mill, and achieves the molecular-level crushing effect, so that the aluminum salt, aluminate and cerium-containing compound are dispersed more uniformly and mixed more fully, and the obtained product has more uniform particle size and pore diameter. The invention strictly controls the pH value of the grinding fluidAt pH < 7.92, the resulting gel is not shaped, and at pH > 9.68, excessive reaction of aluminum ions produces impurities. According to the invention, by controlling the conditions of the gel reaction and the aging reaction, the colloidal particles containing cerium and aluminum elements grow and become larger gradually, the structure of the colloidal particles is more uniform and stable, and CeO is improved 2 And gamma-Al 2 O 3 Is used to avoid structural collapse of the oxide at high temperatures. The metal composite oxide prepared by the invention has the advantages of large specific surface area, large pore volume and large pore diameter. In addition, the preparation method provided by the application has the advantages of wide sources of raw materials, simplicity in operation, low cost, no secondary pollution in the preparation process, environment friendliness and suitability for industrial production and application.
The test results of the examples show that: the metal composite oxide prepared by the invention has typical CeO 2 And gamma-Al 2 O 3 Structure, ceO 2 Loaded to gamma-Al 2 O 3 The surface has large pore volume and large pore diameter, and the structure is loose and layered and porous, and has larger specific surface area.
The invention also provides the application of the metal composite oxide as a catalyst in heavy oil catalytic cracking, and the metal composite oxide as a catalyst has the advantages of large specific surface area, large pore volume and large pore diameter, effectively avoids pore canal blockage caused by macromolecule deposition in heavy oil residues, improves the activity and the use efficiency of the catalyst, can be recycled and has considerable industrial application value.
Drawings
FIG. 1 shows the metal composite oxide CeO of example 1 2 -γAl 2 O 3 An XRD pattern of (b);
FIG. 2 shows the metal composite oxide CeO in example 1 2 -γAl 2 O 3 Is adsorbed by nitrogen to remove the attached drawing;
FIG. 3 shows the metal composite oxide CeO of example 1 2 -γAl 2 O 3 Pore volume and pore diameter distribution map;
FIG. 4 shows the metal composite oxide CeO of example 1 2 -γAl 2 O 3 SEM images of (a);
FIG. 5 is a schematic view of a displayExample 2 Metal composite oxide CeO 2 -γAl 2 O 3 An XRD pattern of (b);
FIG. 6 shows the metal composite oxide CeO in example 2 2 -γAl 2 O 3 Is adsorbed by nitrogen to remove the attached drawing;
FIG. 7 shows the metal composite oxide CeO in example 2 2 -γAl 2 O 3 Pore volume and pore diameter distribution map;
FIG. 8 is a metal composite oxide CeO of example 2 2 -γAl 2 O 3 SEM images of (a);
FIG. 9 shows the metal composite oxide CeO in example 3 2 -γAl 2 O 3 An XRD pattern of (b);
FIG. 10 shows the metal composite oxide CeO in example 3 2 -γAl 2 O 3 Is adsorbed by nitrogen to remove the attached drawing;
FIG. 11 shows the metal composite oxide CeO in example 3 2 -γAl 2 O 3 Pore volume and pore diameter distribution map;
FIG. 12 shows the metal composite oxide CeO in example 3 2 -γAl 2 O 3 SEM image of composite catalyst;
FIG. 13 is gamma-Al of comparative example 1 2 O 3 An XRD pattern of (b);
FIG. 14 is gamma-Al of comparative example 1 2 O 3 Is adsorbed by nitrogen to remove the attached drawing;
FIG. 15 is gamma-Al of comparative example 1 2 O 3 Pore volume and pore diameter distribution map;
FIG. 16 is gamma-Al of comparative example 1 2 O 3 SEM images of (a).
Detailed Description
The present invention provides a metal composite oxide comprising CeO 2 And gamma-Al 2 O 3 Composition; the CeO 2 Loaded on the gamma-Al 2 O 3 Is a surface of (2); the CeO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 1:9-3:7;
the specific surface area of the metal composite oxide is more than or equal to 380m 2 Per gram, pore volume is more than or equal to 1.4cm 3 /g, pore size≥14nm。
In the present invention, the CeO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 1:9-3:7, preferably 1:9.
In the present invention, the specific surface area of the metal composite oxide is preferably 380 to 480m 2 Preferably, the pore volume per gram is 1.4-1.8 cm 3 The pore diameter is preferably 14 to 18nm.
In the invention, the metal composite oxide is prepared from the preparation raw materials through colloid milling, pH value adjustment, gel reaction, aging and roasting; in the present invention, the raw materials for preparing the metal composite oxide preferably include aluminum salts, aluminates, and cerium-containing compounds. In the present invention, the preparation raw material preferably further includes water, more preferably pure water or deionized water.
In the present invention, the ratio of the amount of the raw materials for preparing the metal composite oxide is preferably described in detail in the preparation method, and will not be described in detail herein.
The invention provides a preparation method of the metal composite oxide, which comprises the following steps:
mixing aluminum salt, a cerium-containing compound and water to obtain a mixed solution A;
colloid milling is carried out on the mixed solution A and the aluminate solution to obtain grinding solution A;
adjusting the pH value of the grinding fluid A to be alkaline, and performing a gel reaction to obtain a gel system A;
aging the gel system A to obtain cerium-containing pseudo-boehmite A;
and roasting the cerium-containing pseudo-boehmite A to obtain the metal composite oxide.
The invention mixes aluminum salt, cerium compound and water to obtain mixed solution A.
In the present invention, the aluminum salt is Al 2 (SO 4 ) 3 ·18H 2 O、AlCl 3 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 One or more of O; the aluminate is NaAlO 2 And KAlO 2 One or two of the following components; the cerium-containing compound is cerium salt and CeO 2 One or both of the cerium salts including Ce (NO 3 ) 3 ·6H 2 O、CeCl 3 ·7H 2 O、Ce 2 (SO 4 ) 3 ·8H 2 O and (NH) 4 ) 2 Ce(NO 3 ) 6 One or more of the following.
In the present invention, the CeO 2 The preparation method of (2) preferably comprises the following steps: mixing cerium salt, water and inorganic base, and performing precipitation reaction to obtain Ce (OH) 3 The method comprises the steps of carrying out a first treatment on the surface of the The Ce (OH) 3 First roasting to obtain CeO 2 。
The invention mixes cerium salt, water and inorganic alkali, carries out precipitation reaction and obtains Ce (OH) 3 . In the present invention, the inorganic base preferably includes NaOH, KOH and Ca (OH) 2 One or more of the following. In the present invention, the cerium salt is mixed with OH in an inorganic base - The molar ratio of (2) is preferably 1:3 to 6. In the present invention, the cerium salt, water and inorganic base mixture preferably includes: dissolving cerium salt in water to obtain cerium salt solution; dissolving inorganic alkali in water to obtain inorganic alkali solution; mixing the cerium salt solution and an inorganic alkali solution. After the precipitation reaction, the present invention preferably further includes centrifugation, washing and drying.
Obtaining Ce (OH) 3 The present invention then provides the Ce (OH) 3 First roasting to obtain CeO 2 . In the present invention, the temperature of the first firing is preferably 400 to 600 ℃, and the time is preferably 2 to 4 hours. In the present invention, the first firing is preferably performed in a muffle furnace.
In the present invention, the concentration of the aluminum salt in the mixed solution A is preferably 0.2mol/L, and the concentration of the cerium-containing compound is preferably 0.01 to 0.04mol/L.
In the present invention, the aluminum salt, cerium-containing compound and water mixing preferably includes: adding aluminum salt into water, stirring for dissolving, adding cerium-containing compound, and stirring for dissolving.
After the mixed solution A is obtained, colloid milling is carried out on the mixed solution A and aluminate solution to obtain grinding solution A.
In the present invention, the concentration of the aluminate solution is preferably 0.4 to 1.2mol/L. In the polishing liquid a of the present invention, the molar ratio of the aluminum salt, aluminate, and cerium-containing compound is preferably 1:2 to 6:0.01 to 0.04, more preferably 1:3 to 4:0.01 to 0.02.
In the present invention, the colloid mill is preferably performed in a colloid mill apparatus. In the present invention, the rotation speed of the colloid mill is preferably 1000 to 3000r/min, more preferably 2500 to 3000r/min, the temperature is preferably 20 to 25 ℃, the time is preferably 5 to 10min, more preferably 5 to 7min.
After the grinding fluid A is obtained, the pH value of the grinding fluid A is regulated to be alkaline, and a gel reaction is carried out to obtain a gel system A.
In the present invention, the pH of the polishing liquid a is preferably in the range of 7.92 to 9.68. In the present invention, it is preferable to adjust the pH of the polishing liquid a using dilute nitric acid or NaOH solution; the concentration of the dilute nitric acid and NaOH solution is preferably 0.1-0.3 mol/L. In the present invention, the temperature of the gel reaction is preferably 25 to 75 ℃, more preferably 25 to 45 ℃, and the time is preferably 1 to 5 hours, more preferably 2 to 3 hours, and the stirring speed is preferably 100 to 600r/min. In the present invention, the stirring is preferably performed using a magnetic stirrer.
After the gel system A is obtained, the gel system A is aged to obtain the cerium-containing pseudo-boehmite A.
In the present invention, the aging temperature is preferably 25 to 75 ℃, more preferably 45 to 55 ℃, and the time is 1 to 5 hours, more preferably 2 to 3 hours.
In the present invention, the temperature of the gel reaction is < the temperature of aging.
After said aging, the invention preferably further comprises centrifugation, washing, sedimentation and drying.
After obtaining cerium-containing pseudo-boehmite A, the invention calcines the cerium-containing pseudo-boehmite A to obtain the metal composite oxide.
In the present invention, the baking temperature is preferably 400 to 600 ℃, more preferably 400 to 500 ℃, the baking time is 2 to 4 hours, more preferably 2.5 to 3.5 hours, and the heating rate to the baking temperature is preferably 3 to 8 ℃/min. In the present invention, the firing is preferably performed in a muffle furnace.
After the calcination, the present invention preferably further includes cooling and grinding.
The invention also provides another preparation method of the metal composite oxide, which comprises the following steps:
colloid milling is carried out on the aluminum salt solution and the aluminate solution to obtain grinding liquid B;
adjusting the pH value of the grinding fluid B to be alkaline, and performing a gel reaction to obtain a gel system B;
aging the gel system B to obtain pseudo-boehmite B;
the pseudo-boehmite B is subjected to first roasting to obtain gamma-Al 2 O 3 ；
Subjecting the gamma-Al to 2 O 3 Grinding and mixing cerium salt and water, and performing second roasting to obtain the metal composite oxide.
The aluminum salt solution and the aluminate solution are subjected to colloid milling to obtain grinding liquid B.
In the present invention, the aluminum salt is preferably Al 2 (SO 4 ) 3 ·18H 2 O、AlCl 3 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 One or more of O; the aluminate is preferably NaAlO 2 And KAlO 2 One or two of them.
In the present invention, the concentration of the aluminum salt solution is preferably 0.2mol/L. In the present invention, the concentration of the aluminate solution is preferably 0.4 to 1.2mol/L. In the polishing liquid B of the present invention, the molar ratio of the aluminum salt to the aluminate is preferably 1:2 to 6.
In the present invention, the colloid mill is preferably performed in a colloid mill apparatus. In the present invention, the rotation speed of the colloid mill is preferably 1000 to 3000r/min, more preferably 2500 to 3000r/min, the temperature is preferably 20 to 25 ℃, the time is preferably 5 to 10min, more preferably 5 to 7min.
After the grinding fluid B is obtained, the pH value of the grinding fluid B is regulated to be alkaline, and a gel reaction is carried out to obtain a gel system B.
In the present invention, the pH of the polishing liquid B is preferably in the range of 7.92 to 9.68. In the present invention, it is preferable to adjust the pH of the polishing liquid B using dilute nitric acid or NaOH solution; the concentration of the dilute nitric acid and NaOH solution is preferably 0.1-0.3 mol/L. In the present invention, the temperature of the gel reaction is preferably 25 to 75 ℃, more preferably 25 to 45 ℃, and the time is preferably 1 to 5 hours, more preferably 2 to 3 hours, and the stirring speed is preferably 100 to 600r/min. In the present invention, the stirring is preferably performed using a magnetic stirrer.
After the gel system B is obtained, the gel system B is aged in the invention to obtain the pseudo-boehmite B.
In the present invention, the aging temperature is preferably 25 to 75 ℃, more preferably 45 to 55 ℃, and the time is 1 to 5 hours, more preferably 2 to 3 hours.
In the present invention, the temperature of the gel reaction is < the temperature of aging.
After said aging, the invention preferably further comprises centrifugation, washing, sedimentation and drying.
After obtaining pseudo-boehmite B, the invention carries out first roasting on the pseudo-boehmite B to obtain gamma-Al 2 O 3 。
In the present invention, the temperature of the first firing is preferably 400 to 600 ℃, more preferably 400 to 500 ℃, and the firing time is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours. In the present invention, the first firing is preferably performed in a muffle furnace.
After the first firing, the present invention preferably further includes cooling and grinding.
Obtaining gamma-Al 2 O 3 The invention then provides the gamma-Al 2 O 3 Grinding and mixing cerium salt and water, and performing second roasting to obtain the metal composite oxide.
In the present invention, the cerium salt preferably includes Ce (NO 3 ) 3 ·6H 2 O、CeCl 3 ·7H 2 O、Ce 2 (SO 4 ) 3 ·8H 2 O and (NH) 4 ) 2 Ce(NO 3 ) 6 One or more of the following.
In the present invention,the gamma-Al 2 O 3 The ratio of the water to the water is preferably 1g (1.4-1.6) mL; the gamma-Al 2 O 3 The molar ratio of cerium salt is preferably 40:1-4. In the present invention, the gamma-Al 2 O 3 The grinding and mixing of cerium salt and water is preferably carried out under stirring for a period of preferably 4 to 6 hours, so that gamma-Al 2 O 3 And cerium salt are uniformly mixed. In the present invention, it is preferable to further include mixing well gamma-Al 2 O 3 And drying the cerium salt mixture, and then performing second roasting, wherein the drying temperature is preferably 55-65 ℃, and the drying time is preferably 2-4 h.
In the present invention, the temperature of the second firing is preferably 400 to 600 ℃, more preferably 400 to 500 ℃, for preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, and the rate of temperature rise to the temperature of the second firing is preferably 3 to 8 ℃/min. In the present invention, the second firing is preferably performed in a muffle furnace.
After the second firing, the present invention preferably further includes cooling and grinding.
The invention also provides an application of the metal composite oxide or the metal composite oxide prepared by the preparation method in heavy oil catalytic cracking as a catalyst.
The technical solution of the present invention will be further described by the following specific embodiments, and it should be apparent to those skilled in the art that the examples are only for aiding in understanding the present invention and should not be construed as limiting the present invention in any way.
Example 1
4.9182g NaAlO was weighed 2 100mL of deionized water was added to the beaker and dissolved with sufficient stirring to a concentration of 0.6mol/L. 7.5026gAl (NO) 3 ) 3 ·6H 2 O was dissolved in a beaker with 100mL of deionized water under stirring to a concentration of 0.2mol/L, and 0.4530g of Ce (NO) 3 ) 3 .6H 2 O was dissolved by stirring sufficiently at a concentration of 0.01mol/L. Starting colloid mill at 3000r/min, and mixing with NaAlO 2 Solution and Ce (NO) 3 ) 3 .6H 2 Al of O (NO) 3 ) 3 .6H 2 And (3) quickly adding the O solution into a colloid mill in parallel, grinding for about 5min, adjusting the pH value of the grinding liquid to 8.77, placing the grinding liquid in a magnetic stirrer at the rotating speed of 350r/min, performing gel reaction at 25 ℃ for 2h, aging at 45 ℃ for 2h, centrifuging, washing the precipitate, and drying the precipitate in a 60 ℃ oven to obtain the cerium-containing pseudo-boehmite.
The cerium-containing pseudo-boehmite is put into a muffle furnace for roasting, the temperature is increased to 400 ℃ according to 5 ℃/min, the heat is preserved for 3 hours, and then the metal composite oxide CeO is obtained after cooling down 2 -γAl 2 O 3 Wherein, ceO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 1:9.
Example 2
Weighing Ce (NO) 3 ) 3 .6H 2 8.6844g of O solid is placed in a beaker, 200mL of deionized water is added, and the mixture is stirred to be dissolved, and the concentration of the O solid is 0.1mol/L; weighing 2.4g of NaOH solid, placing in a beaker, adding 200mL of deionized water, and fully stirring to dissolve the NaOH solid, wherein the concentration is 0.3mol/L; mixing the above two solutions, stirring for about 15min, standing for 30min, centrifuging the precipitate, washing, oven drying at 60deg.C, oven drying the dried precipitate, oven drying at 5 deg.C/min to 400 deg.C, maintaining the temperature for 3 hr, cooling to obtain CeO 2 。
Weigh 4.9190g NaAlO 2 Adding 100mL of deionized water into a beaker, and fully stirring to dissolve the deionized water, wherein the concentration of the deionized water is 0.6mol/L; 7.4993g of Al (NO) was weighed out separately 3 ) 3 .6H 2 O is added with 100mL of deionized water in a beaker, and is fully stirred to dissolve, al (NO) 3 ) 3 .6H 2 O solution concentration 0.2mol/L; starting colloid mill at 3000r/min, and mixing with NaAlO 2 Solution and Al (NO) 3 ) 3 .6H 2 The O solution was rapidly and co-currently fed to the colloid mill and 0.1795g of CeO as described above was added 2 Grinding the powder for about 5min, regulating the pH value of the grinding fluid to 8.65, placing the grinding fluid in a magnetic stirrer at the rotating speed of 350r/min, performing gel reaction for 2h at 25 ℃, aging for 2h at 45 ℃, centrifuging, washing the precipitate, and drying the precipitate in a 60 ℃ oven to obtain the cerium-containing pseudo-boehmite.
The CeO is contained in the mixture 2 Placing pseudo-boehmite into a muffle furnace at 400 ℃ for roasting for 3 hours, and cooling to obtain the metal composite oxide CeO 2 -γAl 2 O 3 Wherein, ceO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 1:9.
Example 3
4.9195g NaAlO was weighed 2 Adding 100mL of deionized water into a beaker, and fully stirring to dissolve the deionized water, wherein the concentration of the deionized water is 0.6mol/L; 7.4972g of Al (NO) was weighed out separately 3 ) 3 .6H 2 O is added with 100mL of deionized water in a beaker, and is fully stirred to dissolve, al (NO) 3 ) 3 .6H 2 O solution concentration 0.2mol/L; starting colloid mill at 3000r/min, and mixing with NaAlO 2 Solution and Al (NO) 3 ) 3 .6H 2 And (3) quickly adding the O solution into a colloid mill in parallel, grinding for about 5min, adjusting the pH value of the grinding liquid to 8.80, placing the grinding liquid in a magnetic stirrer at the rotating speed of 350r/min, performing gel reaction at 25 ℃ for 2h, aging at 45 ℃ for 2h, centrifuging, washing the precipitate, and drying the precipitate in a 60 ℃ oven to obtain the pseudo-boehmite.
The pseudo-boehmite is put into a muffle furnace at 400 ℃ for roasting for 3 hours, and then cooled to obtain gamma-Al 2 O 3 。
Weighing the gamma-Al 2 O 3 4.0784g in a beaker, 0.4548g Ce (NO 3 ) 3 .6H 2 Adding 6mL of deionized water into O solid, grinding and mixing, placing into a magnetic stirrer for stirring at the rotating speed of 250r/min and the temperature of 25 ℃ for 6 hours, placing into a 60 ℃ oven for drying, placing the dried sample into a muffle furnace for roasting, heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, and cooling to obtain the metal composite oxide CeO 2 -γAl 2 O 3 Wherein, ceO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 1:9.
Example 4
4.9224g NaAlO was weighed 2 100mL of deionized water was added to the beaker and dissolved with sufficient stirring to a concentration of 0.6mol/L. 7.4855gAl (NO) 3 ) 3 ·6H 2 O is added into a beaker, 100mL of deionized water is added, after stirring and dissolution, the concentration is 0.2mol/L, and 1.0214g C is addede(NO 3 ) 3 .6H 2 O was dissolved by stirring sufficiently at a concentration of 0.02mol/L. Starting colloid mill at 3000r/min, and mixing with NaAlO 2 Solution and Ce (NO) 3 ) 3 .6H 2 Al of O (NO) 3 ) 3 .6H 2 And (3) quickly adding the O solution into a colloid mill in parallel, grinding for about 5min, adjusting the pH value of the grinding liquid to 8.70, placing the grinding liquid in a magnetic stirrer at the rotating speed of 350r/min, performing gel reaction at 25 ℃ for 2h, aging at 45 ℃ for 2h, centrifuging, washing the precipitate, and drying the precipitate in a 60 ℃ oven to obtain the cerium-containing pseudo-boehmite.
The cerium-containing pseudo-boehmite is put into a muffle furnace for roasting, the temperature is increased to 400 ℃ according to 5 ℃/min, the heat is preserved for 3 hours, and then the metal composite oxide CeO is obtained after cooling down 2 -γAl 2 O 3 Wherein, ceO 2 And gamma-Al 2 O 3 The mass ratio of (2) to (8).
Example 5
Weighing Ce (NO) 3 ) 3 .6H 2 8.6802g of O solid is placed in a beaker, 200mL of deionized water is added, and the mixture is stirred to be dissolved, and the concentration of the O solid is 0.1mol/L; weighing 2.4g of NaOH solid, placing in a beaker, adding 200mL of deionized water, and fully stirring to dissolve the NaOH solid, wherein the concentration is 0.3mol/L; mixing the above two solutions, stirring for about 15min, standing for 30min, centrifuging the precipitate, washing, oven drying at 60deg.C, oven drying the dried precipitate, oven drying at 5 deg.C/min to 400 deg.C, maintaining the temperature for 3 hr, cooling to obtain CeO 2 。
4.9203g NaAlO was weighed 2 Adding 100mL of deionized water into a beaker, and fully stirring to dissolve the deionized water, wherein the concentration of the deionized water is 0.6mol/L; 7.4762g of Al (NO) was weighed out separately 3 ) 3 .6H 2 O is added with 100mL of deionized water in a beaker, and is fully stirred to dissolve, al (NO) 3 ) 3 .6H 2 O solution concentration 0.2mol/L; starting colloid mill at 3000r/min, and mixing with NaAlO 2 Solution and Al (NO) 3 ) 3 .6H 2 The O solution was rapidly and co-currently fed to the colloid mill and 0.3518g of CeO as described above was added 2 Grinding for about 5min, and adjusting pH of the grinding fluidAnd (3) setting in magnetic stirrer at 350r/min and at 25 deg.c for gel reaction for 2 hr, ageing at 45 deg.c for 2 hr, centrifuging, washing the precipitate, stoving the precipitate in 60 deg.c oven to obtain cerium-containing pseudoboehmite.
The cerium-containing pseudo-boehmite is put into a muffle furnace at 400 ℃ for roasting for 3 hours, and then cooled to obtain the metal composite oxide CeO 2 -γAl 2 O 3 Wherein, ceO 2 And gamma-Al 2 O 3 The mass ratio of (2) to (8).
Example 6
4.9215g NaAlO was weighed 2 Adding 100mL of deionized water into a beaker, and fully stirring to dissolve the deionized water, wherein the concentration of the deionized water is 0.6mol/L; 7.4887g of Al (NO) was weighed out separately 3 ) 3 .6H 2 O is added with 100mL of deionized water in a beaker, and is fully stirred to dissolve, al (NO) 3 ) 3 .6H 2 O solution concentration 0.2mol/L; starting colloid mill at 3000r/min, and mixing with NaAlO 2 Solution and Al (NO) 3 ) 3 .6H 2 And (3) quickly adding the O solution into a colloid mill in parallel, grinding for about 5min, adjusting the pH value of the grinding liquid to 8.78, placing the grinding liquid in a magnetic stirrer at the rotating speed of 350r/min, performing gel reaction at 25 ℃ for 2h, aging at 45 ℃ for 2h, centrifuging, washing the precipitate, and drying the precipitate in a 60 ℃ oven to obtain the pseudo-boehmite.
The pseudo-boehmite is put into a muffle furnace at 400 ℃ for roasting for 3 hours, and then cooled to obtain gamma-Al 2 O 3 。
Weighing the gamma-Al 2 O 3 4.0815g in a beaker, 0.8922g Ce (NO 3 ) 3 .6H 2 Adding 6mL of deionized water into O solid, grinding and mixing, placing into a magnetic stirrer for stirring at the rotating speed of 250r/min and the temperature of 25 ℃ for 6 hours, placing into a 60 ℃ oven for drying, placing the dried sample into a muffle furnace for roasting, heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, and cooling to obtain the metal composite oxide CeO 2 -γAl 2 O 3 Wherein, ceO 2 And gamma-Al 2 O 3 The mass ratio of (2) to (8).
Example 7
4.9215g NaAlO was weighed 2 In a beaker, add100mL of deionized water was added and the mixture was stirred well to dissolve the solution at a concentration of 0.6mol/L. 7.5008gAl (NO) 3 ) 3 ·6H 2 O was dissolved in a beaker with 100mL of deionized water under stirring to a concentration of 0.2mol/L, and 1.7322g of Ce (NO) 3 ) 3 .6H 2 O was dissolved by stirring sufficiently at a concentration of 0.04mol/L. Starting colloid mill at 3000r/min, and mixing with NaAlO 2 Solution and Ce (NO) 3 ) 3 .6H 2 Al of O (NO) 3 ) 3 .6H 2 And (3) quickly adding the O solution into a colloid mill in parallel, grinding for about 5min, adjusting the pH value of the grinding liquid to 8.90, placing the grinding liquid in a magnetic stirrer at the rotating speed of 350r/min, performing gel reaction at 25 ℃ for 2h, aging at 45 ℃ for 2h, centrifuging, washing the precipitate, and drying the precipitate in a 60 ℃ oven to obtain the cerium-containing pseudo-boehmite.
The cerium-containing pseudo-boehmite is put into a muffle furnace for roasting, the temperature is increased to 400 ℃ according to 5 ℃/min, the heat is preserved for 3 hours, and then the metal composite oxide CeO is obtained after cooling down 2 -γAl 2 O 3 Wherein, ceO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 3:7.
Example 8
Weighing Ce (NO) 3 ) 3 .6H 2 8.6818g of O solid is placed in a beaker, 200mL of deionized water is added, and the mixture is stirred to be dissolved, and the concentration of the O solid is 0.1mol/L; weighing 2.4g of NaOH solid, placing in a beaker, adding 200mL of deionized water, and fully stirring to dissolve the NaOH solid, wherein the concentration is 0.3mol/L; mixing the above two solutions, stirring for about 15min, standing for 30min, centrifuging the precipitate, washing, oven drying at 60deg.C, oven drying the dried precipitate, oven drying at 5 deg.C/min to 400 deg.C, maintaining the temperature for 3 hr, cooling to obtain CeO 2 。
4.9175g NaAlO was weighed 2 Adding 100mL of deionized water into a beaker, and fully stirring to dissolve the deionized water, wherein the concentration of the deionized water is 0.6mol/L; 7.4836g of Al (NO) was weighed out separately 3 ) 3 .6H 2 O is added with 100mL of deionized water in a beaker, and is fully stirred to dissolve, al (NO) 3 ) 3 .6H 2 O solution concentration 0.2mol/L; starting the colloid mill at a rotating speed3000r/min, mixing the above NaAlO 2 Solution and Al (NO) 3 ) 3 .6H 2 The O solution was rapidly and co-currently fed to the colloid mill and 0.7205g of CeO as described above was added 2 Grinding the powder for about 5min, regulating the pH value of the grinding fluid to 8.75, placing the grinding fluid in a magnetic stirrer at the rotating speed of 350r/min, performing gel reaction for 2h at 25 ℃, aging for 2h at 45 ℃, centrifuging, washing the precipitate, and drying the precipitate in a 60 ℃ oven to obtain the cerium-containing pseudo-boehmite.
The cerium-containing pseudo-boehmite is put into a muffle furnace at 400 ℃ for roasting for 3 hours, and then cooled to obtain the metal composite oxide CeO 2 -γAl 2 O 3 Wherein, ceO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 3:7.
Example 9
4.9208g NaAlO was weighed 2 Adding 100mL of deionized water into a beaker, and fully stirring to dissolve the deionized water, wherein the concentration of the deionized water is 0.6mol/L; 7.4933g of Al (NO) was weighed out separately 3 ) 3 .6H 2 O is added with 100mL of deionized water in a beaker, and is fully stirred to dissolve, al (NO) 3 ) 3 .6H 2 O solution concentration 0.2mol/L; starting colloid mill at 3000r/min, and mixing with NaAlO 2 Solution and Al (NO) 3 ) 3 .6H 2 And (3) quickly adding the O solution into a colloid mill in parallel, grinding for about 5min, adjusting the pH value of the grinding liquid to 8.82, placing the grinding liquid in a magnetic stirrer at the rotating speed of 350r/min, performing gel reaction at 25 ℃ for 2h, aging at 45 ℃ for 2h, centrifuging, washing the precipitate, and drying the precipitate in a 60 ℃ oven to obtain the pseudo-boehmite.
The pseudo-boehmite is put into a muffle furnace at 400 ℃ for roasting for 3 hours, and then cooled to obtain gamma-Al 2 O 3 。
Weighing the gamma-Al 2 O 3 4.0752g in a beaker, 1.7364g Ce (NO 3 ) 3 .6H 2 Adding 6mL of deionized water into O solid, immersing and mixing, placing the mixture in a magnetic stirrer for stirring at the speed of 250r/min and the temperature of 25 ℃ for 6 hours, placing the mixture in a 60 ℃ oven for drying, placing the dried sample in a muffle furnace for roasting, heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, and cooling to obtain the metal composite oxide CeO 2 -γAl 2 O 3 Wherein, ceO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 3:7.
Comparative example 1
4.9237g NaAlO was weighed out 2 Adding 100mL of deionized water into a beaker, and fully stirring to dissolve the deionized water, wherein the concentration of the deionized water is 0.6mol/L; 7.5014g of Al (NO) 3 ) 3 .6H 2 O is added with 100mL of deionized water in a beaker, and is fully stirred and dissolved, and the concentration of O is 0.2mol/L; starting colloid mill at 3000r/min, and mixing with NaAlO 2 Solution and Al (NO) 3 ) 3 .6H 2 And (3) quickly adding the O solution into a colloid mill in parallel, grinding for about 5min, adjusting the pH value of the grinding liquid to 8.87, placing the grinding liquid in a magnetic stirrer at the rotating speed of 350r/min, performing gel reaction at 25 ℃ for 2h, aging at 45 ℃ for 2h, centrifuging, washing the precipitate, and drying the precipitate in a 60 ℃ oven to obtain the pseudo-boehmite.
The pseudo-boehmite is put into a muffle furnace to be roasted, the temperature is raised to 400 ℃ at 5 ℃/min, the heat is preserved for 3 hours, and then the gamma-Al is obtained after cooling down 2 O 3 。
The invention adopts a 4-station specific surface and porosity adsorption instrument (ASAP-2640-4N) to carry out mesoporous full analysis on the pore structure of the prepared sample, and test items comprise specific surface area, pore volume and pore diameter, and specific test results are shown in Table 1.
Table 1 test data for samples prepared in examples 1 to 9 and comparative example 1
| Sequence number | Product(s) | Specific surface area (m) 2 /g) | Pore volume (cm) 3 /g) | Aperture (nm) |
| Example 1 | CeO 2 -γAl 2 O 3 | 413.7725 | 1.6583 | 16.153 |
| Example 2 | CeO 2 -γAl 2 O 3 | 446.6745 | 1.7417 | 15.597 |
| Example 3 | CeO 2 -γAl 2 O 3 | 392.5617 | 1.4391 | 15.4518 |
| Example 4 | CeO 2 -γAl 2 O 3 | 410.4382 | 1.6518 | 16.0946 |
| Example 5 | CeO 2 -γAl 2 O 3 | 442.8295 | 1.7392 | 15.5733 |
| Example 6 | CeO 2 -γAl 2 O 3 | 391.7154 | 1.4325 | 15.4978 |
| Example 7 | CeO 2 -γAl 2 O 3 | 411.2539 | 1.6475 | 16.0776 |
| Example 8 | CeO 2 -γAl 2 O 3 | 443.7208 | 1.7267 | 15.5649 |
| Example 9 | CeO 2 -γAl 2 O 3 | 390.6855 | 1.4278 | 15.4493 |
| Comparative example 1 | γ-Al 2 O 3 | 303.0521 | 0.6839 | 9.1663 |
The present invention also employs an X-ray diffractometer to determine XRD of samples prepared in examples and comparative examples, the test conditions including: the working voltage is 40kV, the tube current is 30mA, the step measurement is carried out, the initial angle is 5 degrees, the end angle is 75 degrees, the step angle is 0.02 degrees, the K alpha radiation source and the Cu target are adopted, and the test result is shown in the attached drawing of the specification.
FIGS. 1, 5 and 9 show the metal composite oxide CeO obtained in examples 1 to 3 2 -γAl 2 O 3 As can be seen from the XRD patterns of FIGS. 1, 5 and 9, gamma-Al 2 O 3 Characteristic peaks at 2θ=36.5 °, 46.3 ° and 67 °, typical γ -Al 2 O 3 A crystalline form; ceO (CeO) 2 Characteristic peaks at 2θ=28.5°, 36.5 °, 47.5 ° and 56.3 ° are typical CeO 2 Crystal form, which illustrates CeO in the metal composite oxide prepared by the application 2 Successfully load to gamma-Al 2 O 3 And (3) on a carrier.
FIGS. 2, 6 and 10 show the metal composite oxide CeO obtained in examples 1 to 3 2 -γAl 2 O 3 The nitrogen adsorption desorption isotherm in fig. 2, 6 and 10 belongs to the hysteresis loop of type IV, type H2 in the type of physical adsorption isotherm proposed by IUPAC, and the adsorption desorption line is in the medium pressure zone (P/P 0 =0.6 to 0.9), capillary condensation occurs, and obvious hysteresis loops appear, which indicates that a mesoporous structure exists in the sample.
FIGS. 3, 7 and 11 show the metal composite oxide CeO obtained in examples 1 to 3 2 -γAl 2 O 3 As can be seen from FIGS. 3, 7 and 11, 1.4cm in pore volume and pore diameter distribution 3 The pore size corresponding to the pore volume above/g is basically more than or equal to 14nm, which indicates that the metal composite oxide prepared by the invention has the characteristics of large pore volume and large pore diameter.
FIGS. 4, 8 and 12 show the metal composite oxide CeO obtained in examples 1 to 3 2 -γAl 2 O 3 As can be seen from the SEM images of fig. 4, 8 and 12, the morphology of the metal composite oxide sample is lamellar and porous, illustrating CeO 2 Loaded to gamma-Al 2 O 3 The pore volume and the pore diameter of the sample are increased, the sample is in loose layers and holes, and the specific surface area of the sample is increased.
FIG. 13 shows the gamma obtained in comparative example 1-Al 2 O 3 As can be seen from FIG. 13, gamma-Al 2 O 3 Characteristic peaks at 2θ=34.9 °, 36.5 °, 46.3 °, 67 °, and is typically γ -Al 2 O 3 And (5) a crystal form.
FIG. 14 shows the gamma-Al obtained in comparative example 1 2 O 3 The nitrogen adsorption desorption isotherm of figure 14 belongs to the IV type, the H2 type hysteresis loop in the type of the physical adsorption isotherm proposed by IUPAC, and the adsorption desorption line is in a medium pressure zone (P/P 0 =0.45 to 0.9), capillary condensation occurs, and obvious hysteresis loops appear, which indicates that a mesoporous structure exists in the sample.
FIG. 15 shows the gamma-Al obtained in comparative example 1 2 O 3 As can be seen from FIG. 15, the pore volume and pore diameter distribution of (C) is shown in FIG. 15 2 O 3 The pore volume of (2) is less than 1cm 3 And/g, which is significantly smaller than the pore volume and pore diameter of the metal composite oxides prepared in examples 1 to 3.
FIG. 16 shows the gamma-Al obtained in comparative example 1 2 O 3 As can be seen from the SEM image of FIG. 16, gamma-Al 2 O 3 The particles are compact and have a block structure, and the agglomeration phenomenon exists.
As is apparent from comparison of pore volume and pore diameter distribution diagrams and SEM images of the samples obtained in examples 1 to 3 and comparative example 1, the metal composite oxides, ceO, obtained in examples 1 to 3 2 Loaded to gamma-Al 2 O 3 The surface has large pore volume and large pore diameter, and the structure is loose and layered and porous, and has larger specific surface area.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A metal composite oxide comprising CeO 2 And gamma-Al 2 O 3 Composition; the CeO 2 Loaded on the gamma-Al 2 O 3 Is a surface of (2); the CeO 2 And gamma-Al 2 O 3 The mass ratio of (2) is 1:9-3:7;
the specific surface area of the metal composite oxide is more than or equal to 380m 2 Per gram, pore volume is more than or equal to 1.4cm 3 And/g, the pore diameter is more than or equal to 14nm.
2. The metal composite oxide according to claim 1, wherein the metal composite oxide is obtained by colloid milling, pH adjustment, gel reaction, aging and calcination of a preparation raw material; the preparation raw materials comprise aluminum salt, aluminate and cerium-containing compound.
3. The method for producing a metal composite oxide according to any one of claims 1 to 2, characterized by comprising the steps of:
mixing aluminum salt, a cerium-containing compound and water to obtain a mixed solution A;
colloid milling is carried out on the mixed solution A and the aluminate solution to obtain grinding solution A;
adjusting the pH value of the grinding fluid A to be alkaline, and performing a gel reaction to obtain a gel system A;
aging the gel system A to obtain cerium-containing pseudo-boehmite A;
and roasting the cerium-containing pseudo-boehmite A to obtain the metal composite oxide.
4. The method according to claim 3, wherein the aluminum salt is Al 2 (SO 4 ) 3 ·18H 2 O、AlCl 3 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 One or more of O; the aluminate is NaAlO 2 And KAlO 2 One or two of the following components; the cerium-containing compound is cerium salt and CeO 2 One or both of the cerium salts including Ce (NO 3 ) 3 ·6H 2 O、CeCl 3 ·7H 2 O、Ce 2 (SO 4 ) 3 ·8H 2 O and (NH) 4 ) 2 Ce(NO 3 ) 6 One of the followingOr a plurality thereof.
5. The preparation method according to claim 3 and 4, wherein the molar ratio of aluminum salt, aluminate and cerium-containing compound in the polishing liquid A is 1:2-6:0.01-0.04;
the rotating speed of the colloid mill is 1000-3000 r/min, the temperature is 20-25 ℃ and the time is 5-10 min;
the pH value range is 7.92-9.68;
the temperature of the gel reaction is 25-75 ℃, the time is 1-5 h, and the stirring speed is 100-600 r/min;
the aging temperature is 25-75 ℃ and the aging time is 1-5 h;
the temperature of the gel reaction is less than the aging temperature;
the roasting temperature is 400-600 ℃, and the roasting time is 2-4 h.
6. The method according to claim 4, wherein the CeO 2 The preparation method of the (C) comprises the following steps:
mixing cerium salt, water and inorganic base, and performing precipitation reaction to obtain Ce (OH) 3 ；
The Ce (OH) 3 First roasting to obtain CeO 2 。
The inorganic base comprises NaOH, KOH and Ca (OH) 2 One or more of the following; OH in the cerium salt and inorganic base - The molar ratio of (2) is 1:3-6;
the temperature of the first roasting is 400-600 ℃ and the time is 2-4 h.
7. The method for producing a metal composite oxide according to any one of claims 1 to 2, characterized by comprising the steps of:
colloid milling is carried out on the aluminum salt solution and the aluminate solution to obtain grinding liquid B;
adjusting the pH value of the grinding fluid B to be alkaline, and performing a gel reaction to obtain a gel system B;
aging the gel system B to obtain pseudo-boehmite B;
the pseudo-boehmite B is subjected to first roasting to obtain gamma-Al 2 O 3 ；
Subjecting the gamma-Al to 2 O 3 Grinding and mixing cerium salt and water, and performing second roasting to obtain the metal composite oxide.
8. The method according to claim 7, wherein the aluminum salt is Al 2 (SO 4 ) 3 ·18H 2 O、AlCl 3 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 One or more of O; the aluminate is NaAlO 2 And KAlO 2 One or two of the following components; the cerium salt includes Ce (NO) 3 ) 3 ·6H 2 O、CeCl 3 ·7H 2 O、Ce 2 (SO 4 ) 3 ·8H 2 O and (NH) 4 ) 2 Ce(NO 3 ) 6 One or more of the following.
9. The method according to claim 7, wherein the molar ratio of aluminum salt to aluminate in the polishing slurry B is 1:2-6;
the rotating speed of the colloid mill is 1000-3000 r/min, the temperature is 20-25 ℃ and the time is 5-10 min;
the pH value range is 7.92-9.68;
the temperature of the gel reaction is 25-75 ℃, the time is 1-5 h, and the stirring speed is 100-600 r/min;
the aging temperature is 25-75 ℃ and the aging time is 1-5 h;
the temperature of the gel reaction is less than the aging temperature;
the temperature of the first roasting is 400-600 ℃ and the time is 2-4 h;
the gamma-Al 2 O 3 The ratio of the water to the water is 1g (1.4-1.6) mL; the gamma-Al 2 O 3 And cerium salt in the molar ratio of 40:1-4;
the temperature of the second roasting is 400-600 ℃ and the time is 2-4 h.
10. Use of the metal composite oxide according to any one of claims 1 to 2 or the metal composite oxide produced by the production method according to any one of claims 3 to 9 as a catalyst in catalytic cracking of heavy oil.
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