CN117299229B - Oil column forming method of catalyst carrier - Google Patents
Oil column forming method of catalyst carrier Download PDFInfo
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- CN117299229B CN117299229B CN202311599621.1A CN202311599621A CN117299229B CN 117299229 B CN117299229 B CN 117299229B CN 202311599621 A CN202311599621 A CN 202311599621A CN 117299229 B CN117299229 B CN 117299229B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000003921 oil Substances 0.000 claims description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 235000019441 ethanol Nutrition 0.000 claims description 26
- 239000003607 modifier Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 239000001632 sodium acetate Substances 0.000 claims description 14
- 235000017281 sodium acetate Nutrition 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- UUGLSEIATNSHRI-UHFFFAOYSA-N 1,3,4,6-tetrakis(hydroxymethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound OCN1C(=O)N(CO)C2C1N(CO)C(=O)N2CO UUGLSEIATNSHRI-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 241001122767 Theaceae Species 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 10
- 235000013824 polyphenols Nutrition 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 7
- 238000001935 peptisation Methods 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 2
- 239000010721 machine oil Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
Abstract
The invention discloses a method for forming an oil column of a catalyst carrier, which relates to the technical field of catalysts and comprises the following steps: step S1, preparing a precursor; s2, preparing sol; and S3, oil column forming. The oil column forming method of the catalyst carrier is simple and easy to implement, and the prepared catalyst carrier is environment-friendly, low in stacking density and high in crushing strength.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an oil column forming method of a catalyst carrier.
Background
The carrier is an important component of the catalyst, and a proper catalyst carrier can increase the effective surface and provide proper pore structure, can improve the mechanical strength of the catalyst and the thermal stability of the catalyst, and can also provide the active center of the catalyst. Sometimes the support may also interact with the active ingredient to form new compounds, resulting in good catalytic effects. Alumina is widely used as a carrier of petrochemical catalysts, such as dehydrogenation catalysts and hydrogenation catalysts, due to its excellent characteristics of high specific surface area, good adsorptivity, thermal stability, surface acidity, etc.
The current method for industrially producing the alumina carrier comprises a spray drying forming method, a rolling ball forming method, an oil column forming method and an oil ammonia column forming method. Compared with other methods, the alumina produced by the oil column forming method has good sphericity, smooth surface and high crushing strength. However, the alumina carrier prepared by the existing oil column forming method has the technical defects of poor hydrothermal stability, higher impurity content, insufficient strength, poor sphericity and lower pore volume.
In order to solve the above problems, chinese patent application publication No. CN111792659a (application publication No. 2020.10.20) discloses a method for preparing spherical alumina by oil column forming process, mixing alumina sol and gelatinizer, dripping into hot oil by dispersing dropper to form, aging, washing, drying, calcining to obtain spherical alumina particles, adding one or more of pseudo-boehmite powder and activated carbon into the alumina sol, soaking the aged gel spheres in one or more of sodium silicate aqueous solution and trisodium phosphate aqueous solution, washing, drying, and calcining. The method does not cause secondary environmental pollution, and the obtained spherical alumina has bulk densityNot more than 0.45g/cm 3 The average crushing strength is not lower than 40N, and the spherical alumina can be used as a catalyst or a carrier and widely applied to the petrochemical industry or the fine chemical industry field. However, the average crush strength of the alumina produced by this method still remains to be further improved and the impurity content remains to be further reduced.
As can be seen, there remains a need in the art for a method of oil column formation for catalyst supports having low bulk density and high crush strength.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an oil column forming method of a catalyst carrier with low bulk density and high crushing strength.
In order to achieve the above purpose, the invention adopts the following technical scheme: an oil column forming method of a catalyst carrier comprises the following steps:
step S1, preparing a precursor: dispersing an aluminum source and a silicon source in an alcohol solvent, uniformly stirring, slowly adding sodium acetate, vigorously stirring for 2 hours, transferring the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and reacting for 14-22 hours at 180-220 ℃; cooling, repeatedly washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 70-80deg.C for 10-20 hr;
step S2, preparing sol: after uniformly dispersing the precursor prepared in the step S1 in water, adding acid liquor to carry out peptization, controlling the pH value of the sol to be 2-5 and the dry-basis solid content to be 20-50wt%; obtaining sol to be formed;
step S3, oil column forming: uniformly mixing the sol to be formed and the modifier, dripping the mixture into a formed oil column through a dispersing dropper for forming, separating formed microspheres, aging, washing with water until no obvious oil stain is formed on the surface, drying and roasting to obtain a catalyst carrier finished product; the modifier comprises the following components in parts by weight: 3-5 parts of urea, 5-10 parts of hexamethylenetetramine, 15-25 parts of tetramethylol glycoluril and 1-3 parts of tea polyphenol.
Preferably, in step S1, the aluminum source is at least one of aluminum sulfate, aluminum nitrate, and aluminum chloride.
Preferably, in step S1, the silicon source is at least one of water glass and silicon tetrachloride; the alcohol solvent is at least one of ethanol, glycerol and isopropanol.
Preferably, in the step S1, the mass ratio of the aluminum source, the silicon source, the alcohol solvent and the sodium acetate is 1 (0.01-0.1): 10-20): 3.
Preferably, the acid solution in the step S2 is an aqueous solution of nitric acid, hydrochloric acid, sulfuric acid or formic acid with a mass percentage concentration of 5-30%.
Preferably, in the step S3, the mass ratio of the sol to be formed to the modifier is 100 (0.1-0.6).
Preferably, the temperature of the molding oil column in the step S3 is 90-99 ℃, and the molding oil is at least one of white oil, mechanical oil and spindle oil.
Preferably, the temperature of the aging in step S3 is 110-160 ℃ and the time is 10-50h.
Preferably, the drying in step S3 is carried out at a temperature of 95-135℃for a period of 6-18 hours.
Preferably, the roasting temperature in the step S3 is 650-1060 ℃ and the time is 6-10h.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) According to the oil column forming method of the catalyst carrier, disclosed by the invention, the precursor is prepared through the hydrothermal reaction, the mixing of the aluminum element and the silicon element with molecular size is realized, the silicon-containing aluminum oxide precursor with complete crystal form, uniform particle size distribution and good dispersibility is formed, the advantages of low impurity content and high crushing resistance strength of a final product can be endowed, and the advantages of higher surface acidity and specific surface area and more flexible adjustment of the prepared catalyst carrier can be endowed through reasonable selection of the aluminum-silicon ratio.
(2) The invention discloses an oil column forming method of a catalyst carrier, which comprises the steps of mixing sol to be formed and a modifier before oil column forming, wherein the modifier comprises the following components in parts by weight: 3-5 parts of urea, 5-10 parts of hexamethylenetetramine, 15-25 parts of tetramethylol glycoluril and 1-3 parts of tea polyphenol. Through reasonable selection of the composition formula of the modifier, the components can be mutually matched to ensure that the sol has better stability, the microscopic particles of the formed spheres are distributed more uniformly, and the sphericity of the spheres is better; the method is matched with the technological parameters of other forming steps, so that the advantages of low bulk density and high crushing strength of the final product are provided.
(3) According to the oil column forming method of the catalyst carrier, the final product has low bulk density and high crushing strength through reasonable selection of the technological parameters of each step; the method has the advantages of high efficiency, good effect, no environmental pollution, small dependence on equipment, simple process steps and low cost, is suitable for mass production and application, and has higher popularization and application values.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
An oil column forming method of a catalyst carrier comprises the following steps:
step S1, preparing a precursor: dispersing an aluminum source and a silicon source in an alcohol solvent, uniformly stirring, slowly adding sodium acetate, vigorously stirring for 2 hours, transferring the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and reacting for 14 hours at 180 ℃; cooling, repeatedly washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 70 ℃ for 10 hours;
step S2, preparing sol: after uniformly dispersing the precursor prepared in the step S1 in water, adding acid liquor to carry out peptization, controlling the pH value of the sol to be 2 and controlling the dry-basis solid content to be 20wt%; obtaining sol to be formed;
step S3, oil column forming: uniformly mixing the sol to be formed and the modifier, dripping the mixture into a formed oil column through a dispersing dropper for forming, separating formed microspheres, aging, washing with water until no obvious oil stain is formed on the surface, drying and roasting to obtain a catalyst carrier finished product; the modifier comprises the following components in parts by weight: 3 parts of urea, 5 parts of hexamethylenetetramine, 15 parts of tetramethylol glycoluril and 1 part of tea polyphenol.
The aluminum source in the step S1 is aluminum sulfate; the silicon source is water glass; the alcohol solvent is ethanol; in the step S1, the mass ratio of the aluminum source to the silicon source to the alcohol solvent to the sodium acetate is 1:0.03:13:3.
The acid liquor in the step S2 is nitric acid aqueous solution with the mass percentage concentration of 12%; in the step S3, the mass ratio of the sol to be formed to the modifier is 100:0.1; and in the step S3, the temperature of the molding oil column is 90 ℃, and the molding oil is white oil.
The aging temperature in the step S3 is 110 ℃ and the aging time is 10 hours; the temperature of the drying in the step S3 is 95 ℃ and the time is 6 hours; the roasting temperature in the step S3 is 650 ℃ and the time is 6 hours.
Example 2
An oil column forming method of a catalyst carrier comprises the following steps:
step S1, preparing a precursor: dispersing an aluminum source and a silicon source in an alcohol solvent, uniformly stirring, slowly adding sodium acetate, vigorously stirring for 2 hours, transferring the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and reacting for 16 hours at 190 ℃; cooling, repeatedly washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 73 ℃ for 13 hours;
step S2, preparing sol: after uniformly dispersing the precursor prepared in the step S1 in water, adding acid liquor to carry out peptization, controlling the pH value of the sol to be 3 and controlling the dry-basis solid content to be 30wt%; obtaining sol to be formed;
step S3, oil column forming: uniformly mixing the sol to be formed and the modifier, dripping the mixture into a formed oil column through a dispersing dropper for forming, separating formed microspheres, aging, washing with water until no obvious oil stain is formed on the surface, drying and roasting to obtain a catalyst carrier finished product; the modifier comprises the following components in parts by weight: 3.5 parts of urea, 6 parts of hexamethylenetetramine, 17 parts of tetramethylol glycoluril and 1.5 parts of tea polyphenol.
In the step S1, the aluminum source is aluminum nitrate; the silicon source in the step S1 is silicon tetrachloride; the alcohol solvent is glycerol; in the step S1, the mass ratio of the aluminum source to the silicon source to the alcohol solvent to the sodium acetate is 1:0.05:13:3; in the step S2, the acid liquid is an aqueous solution of nitric acid, hydrochloric acid, sulfuric acid or formic acid with the mass percentage concentration of 13%.
In the step S3, the mass ratio of the sol to be formed to the modifier is 100:0.25; in the step S3, the temperature of the molding oil column is 93 ℃, and the molding oil is mechanical oil; the aging temperature in the step S3 is 130 ℃ and the time is 25 hours; the temperature of the drying in the step S3 is 110 ℃ and the time is 10 hours; the roasting temperature in the step S3 is 800 ℃ and the time is 7 hours.
Example 3
An oil column forming method of a catalyst carrier comprises the following steps:
step S1, preparing a precursor: dispersing an aluminum source and a silicon source in an alcohol solvent, uniformly stirring, slowly adding sodium acetate, vigorously stirring for 2 hours, transferring the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and reacting for 19 hours at 200 ℃; cooling, repeatedly washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 75 ℃ for 15 hours;
step S2, preparing sol: after uniformly dispersing the precursor prepared in the step S1 in water, adding acid liquor to carry out peptization, controlling the pH value of the sol to be 3.5 and controlling the dry-basis solid content to be 35wt%; obtaining sol to be formed;
step S3, oil column forming: uniformly mixing the sol to be formed and the modifier, dripping the mixture into a formed oil column through a dispersing dropper for forming, separating formed microspheres, aging, washing with water until no obvious oil stain is formed on the surface, drying and roasting to obtain a catalyst carrier finished product; the modifier comprises the following components in parts by weight: 4 parts of urea, 7.5 parts of hexamethylenetetramine, 20 parts of tetramethylol glycoluril and 2 parts of tea polyphenol.
The aluminum source in the step S1 is aluminum chloride; the silicon source is water glass; the alcohol solvent is isopropanol; the mass ratio of the aluminum source to the silicon source to the alcohol solvent to the sodium acetate is 1:0.07:15:3.
The acid liquor in the step S2 is sulfuric acid aqueous solution with the mass percentage concentration of 18%; in the step S3, the mass ratio of the sol to be formed to the modifier is 100:0.4; the temperature of the molding oil column in the step S3 is 95 ℃, and the molding oil is spindle oil; the aging temperature in the step S3 is 130 ℃ and the aging time is 30 hours; the temperature of the drying in the step S3 is 120 ℃ and the time is 12 hours; the roasting temperature in the step S3 is 860 ℃ and the time is 8 hours.
Example 4
An oil column forming method of a catalyst carrier comprises the following steps:
step S1, preparing a precursor: dispersing an aluminum source and a silicon source in an alcohol solvent, uniformly stirring, slowly adding sodium acetate, vigorously stirring for 2 hours, transferring the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and reacting at 210 ℃ for 21 hours; cooling, repeatedly washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 78 ℃ for 18 hours;
step S2, preparing sol: after uniformly dispersing the precursor prepared in the step S1 in water, adding acid liquor to carry out peptization, controlling the pH value of the sol to be 4.5 and controlling the dry-basis solid content to be 45wt%; obtaining sol to be formed;
step S3, oil column forming: uniformly mixing the sol to be formed and the modifier, dripping the mixture into a formed oil column through a dispersing dropper for forming, separating formed microspheres, aging, washing with water until no obvious oil stain is formed on the surface, drying and roasting to obtain a catalyst carrier finished product; the modifier comprises the following components in parts by weight: 4.5 parts of urea, 9 parts of hexamethylenetetramine, 23 parts of tetramethylol glycoluril and 2.5 parts of tea polyphenol.
In the step S1, the aluminum source is a mixture formed by mixing aluminum sulfate, aluminum nitrate and aluminum chloride according to a mass ratio of 1:3:5; the silicon source is a mixture formed by mixing water glass and silicon tetrachloride according to a mass ratio of 1:2; the alcohol solvent is a mixture formed by mixing ethanol, glycerol and isopropanol according to a mass ratio of 1:3:2; in the step S1, the mass ratio of the aluminum source to the silicon source to the alcohol solvent to the sodium acetate is 1:0.08:18:3; the acid liquor in the step S2 is an aqueous solution of nitric acid, hydrochloric acid, sulfuric acid or formic acid with the mass percentage concentration of 26%.
In the step S3, the mass ratio of the sol to be formed to the modifier is 100:0.5; in the step S3, the temperature of the molding oil column is 97 ℃, and the molding oil is white oil; the aging temperature in the step S3 is 150 ℃ and the aging time is 40 hours; the temperature of the drying in the step S3 is 125 ℃ and the time is 16 hours; the roasting temperature in the step S3 is 960 ℃, and the time is 9.5h.
Example 5
An oil column forming method of a catalyst carrier comprises the following steps:
step S1, preparing a precursor: dispersing an aluminum source and a silicon source in an alcohol solvent, uniformly stirring, slowly adding sodium acetate, vigorously stirring for 2 hours, transferring the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and reacting for 22 hours at 220 ℃; cooling, repeatedly washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 80 ℃ for 20 hours;
step S2, preparing sol: after uniformly dispersing the precursor prepared in the step S1 in water, adding acid liquor to carry out peptization, controlling the pH value of the sol to be 5 and controlling the dry-basis solid content to be 50wt%; obtaining sol to be formed;
step S3, oil column forming: uniformly mixing the sol to be formed and the modifier, dripping the mixture into a formed oil column through a dispersing dropper for forming, separating formed microspheres, aging, washing with water until no obvious oil stain is formed on the surface, drying and roasting to obtain a catalyst carrier finished product; the modifier comprises the following components in parts by weight: 5 parts of urea, 10 parts of hexamethylenetetramine, 25 parts of tetramethylol glycoluril and 3 parts of tea polyphenol.
The aluminum source in the step S1 is aluminum chloride; the silicon source is water glass; the alcohol solvent is ethanol; the mass ratio of the aluminum source to the silicon source to the alcohol solvent to the sodium acetate is 1:0.1:20:3; the acid liquor in the step S2 is nitric acid aqueous solution with the mass percentage concentration of 30%.
In the step S3, the mass ratio of the sol to be formed to the modifier is 100:0.6; in the step S3, the temperature of the molding oil column is 99 ℃, and the molding oil is mechanical oil; the aging temperature in the step S3 is 160 ℃ and the aging time is 50 hours; the temperature of the drying in the step S3 is 135 ℃ and the time is 18 hours; the roasting temperature in the step S3 is 1060 ℃ and the time is 10h.
Comparative example 1
This example provides a method for forming an oil column of a catalyst carrier, which is substantially the same as in example 1, except that pseudo-boehmite (produced by winzhou fine crystal alumina limited, dry basis weight content 70%) is used instead of the precursor prepared in step S1.
Comparative example 2
This example provides a method of oil column formation of a catalyst support, substantially the same as example 1, except that the modifier does not contain tetramethylol glycoluril and tea polyphenols.
To further illustrate the beneficial technical effects of the oil column molding method of the catalyst carrier according to each embodiment of the present invention, the catalyst carriers manufactured by the oil column molding methods of the catalyst carriers according to examples 1 to 5 and comparative examples 1 to 2 were subjected to the relevant performance test; the test method is as follows: the bulk density test is to fill a certain amount of sample into a 100mL measuring cylinder, read the volume after compaction, and calculate the ratio of mass to volume to obtain the bulk density. The crushing strength test is to randomly select 50 samples for each case, and take the arithmetic average value after measuring the crushing strength particle by particle.
TABLE 1
| Project | Bulk density of | Crush strength |
| Unit (B) | g/cm 3 | N |
| Example 1 | 0.36 | 60 |
| Example 2 | 0.32 | 62 |
| Example 3 | 0.30 | 63 |
| Example 4 | 0.29 | 66 |
| Example 5 | 0.26 | 67 |
| Comparative example 1 | 0.48 | 53 |
| Comparative example 2 | 0.40 | 57 |
As can be seen from table 1, the catalyst carrier produced by the oil column molding method of the catalyst carrier according to the embodiments of the present invention has higher crush strength and lower push-through density, and the use of the precursor, the tetramethylol glycoluril and the tea polyphenol is beneficial for improving the above properties.
The above embodiments are provided for illustrating the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the present invention and to implement the same, and are not intended to limit the scope of the present invention, but any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. The oil column forming method of the catalyst carrier is characterized by comprising the following steps:
step S1, preparing a precursor: dispersing an aluminum source and a silicon source in an alcohol solvent, uniformly stirring, slowly adding sodium acetate, vigorously stirring for 2 hours, transferring the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and reacting for 14-22 hours at 180-220 ℃; cooling, repeatedly washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 70-80deg.C for 10-20 hr; the mass ratio of the aluminum source to the silicon source to the alcohol solvent to the sodium acetate is 1 (0.01-0.1) (10-20) to 3;
step S2, preparing sol: after uniformly dispersing the precursor prepared in the step S1 in water, adding acid liquor to carry out peptization, controlling the pH value of the sol to be 2-5 and the dry-basis solid content to be 20-50wt%; obtaining sol to be formed;
step S3, oil column forming: uniformly mixing the sol to be formed and the modifier, dripping the mixture into a formed oil column through a dispersing dropper for forming, separating formed microspheres, aging, washing with water until no obvious oil stain is formed on the surface, drying and roasting to obtain a catalyst carrier finished product; the modifier comprises the following components in parts by weight: 3-5 parts of urea, 5-10 parts of hexamethylenetetramine, 15-25 parts of tetramethylol glycoluril and 1-3 parts of tea polyphenol; the mass ratio of the sol to be formed and the modifier is 100 (0.1-0.6).
2. The method for forming an oil column of a catalyst carrier according to claim 1, wherein the aluminum source in step S1 is at least one of aluminum sulfate, aluminum nitrate, and aluminum chloride.
3. The method for forming an oil column of a catalyst carrier according to claim 1, wherein the silicon source in the step S1 is at least one of water glass and silicon tetrachloride; the alcohol solvent is at least one of ethanol, glycerol and isopropanol.
4. The method for forming an oil column of a catalyst carrier according to claim 1, wherein the acid solution in the step S2 is an aqueous solution of nitric acid, hydrochloric acid, sulfuric acid or formic acid with a mass percentage concentration of 5-30%.
5. The method for forming an oil column of a catalyst carrier according to claim 1, wherein the temperature of the formed oil column in step S3 is 90-99 ℃, and the formed oil is at least one of white oil, machine oil, and spindle oil.
6. The method for forming an oil column of a catalyst carrier according to claim 1, wherein the aging temperature in step S3 is 110 to 160 ℃ for 10 to 50 hours.
7. The method for forming an oil column of a catalyst carrier according to claim 1, wherein the drying temperature in step S3 is 95-135 ℃ for 6-18 hours.
8. The method for forming an oil column of a catalyst carrier according to claim 1, wherein the baking temperature in step S3 is 650 to 1060 ℃ for 6 to 10 hours.
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| CN111792659A (en) * | 2020-06-24 | 2020-10-20 | 黎明化工研究设计院有限责任公司 | Method for preparing spherical alumina by oil column molding process |
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| EP1044610A1 (en) * | 1999-04-13 | 2000-10-18 | Basf Aktiengesellschaft | Compositions with sliver on zinc silicate carriers and antibiotic properties |
| CN111792659A (en) * | 2020-06-24 | 2020-10-20 | 黎明化工研究设计院有限责任公司 | Method for preparing spherical alumina by oil column molding process |
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