CN115571902B - Method for improving weather resistance of pseudo-boehmite carrier - Google Patents
Method for improving weather resistance of pseudo-boehmite carrier Download PDFInfo
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- CN115571902B CN115571902B CN202211094900.8A CN202211094900A CN115571902B CN 115571902 B CN115571902 B CN 115571902B CN 202211094900 A CN202211094900 A CN 202211094900A CN 115571902 B CN115571902 B CN 115571902B
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 75
- 238000011282 treatment Methods 0.000 claims abstract description 66
- 239000007788 liquid Substances 0.000 claims abstract description 57
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 54
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 45
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 26
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 26
- 239000000376 reactant Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 238000010257 thawing Methods 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 20
- -1 rare earth chloride Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 12
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical group Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000000703 high-speed centrifugation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 21
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for improving weather resistance of a pseudo-boehmite carrier, which relates to the technical field of pseudo-boehmite and comprises the following steps: (1) modifying kaolin; (2) obtaining a mixed solution; (3) obtaining a treatment mixed solution; (4) preparing sodium hydroxide solution; (5) obtaining sodium metaaluminate solution; (6) obtaining a reactant; (7) obtaining a pseudo-boehmite carrier; according to the method, the pseudo-boehmite of the pompon-shaped aggregate can be prepared, and the pompon-shaped aggregate has a more complex pore structure, so that the pore volume structure in the pseudo-boehmite is greatly improved, and meanwhile, the heat-resistant stability of the prepared pseudo-boehmite carrier is obviously improved by adopting the treatment mixed liquid prepared from the modified kaolin as a reaction liquid, so that the weather resistance of the pseudo-boehmite is obviously improved.
Description
Technical Field
The invention belongs to the technical field of pseudo-boehmite, and in particular relates to a method for improving weather resistance of a pseudo-boehmite carrier.
Background
Pseudoboehmite (PB), of the formula AlOOH nH2O (n=0.08-0.62), is generally considered to be boehmite (boehmite), also known as pseudoboehmite or amorphous aluminum hydroxide, which is not completely crystallized. Pseudo-boehmite is a white powder with a space network structure, and has strong dispersibility, good peptization performance, high specific surface and large porosity.
In the prior art, application number 201610891888.1, the invention provides a preparation method of high-purity pseudo-boehmite, which comprises the following preparation steps: (1) preparing aluminum alkoxide, (2) filtering, (3) carrying out hydrolysis reaction, (4) carrying out alcohol separation, (5) aging and alcohol distillation, (6) filtering and drying to obtain the high-purity pseudo-boehmite. The pseudo-boehmite product prepared by the invention has the advantages of low impurity content, concentrated pore distribution, stable product and the like. The preparation process is environment-friendly, no three wastes are discharged, the recovered alcohol and solvent can be recycled after being treated, and the obtained product can be widely applied to carriers for catalytic reforming and catalytic hydrogenation. The high-purity pseudo-boehmite prepared by the prior art has poor weather resistance, particularly poor heat resistance, is easy to lose water rapidly under the environment of high temperature, causes the damage of stability, and cannot keep good carrier performance.
Accordingly, there is a need for further improvements in the art.
Disclosure of Invention
The invention aims to provide a method for improving weather resistance of a pseudo-boehmite carrier so as to solve the defects in the prior art.
The technical scheme adopted by the invention is as follows:
a method for improving weatherability of pseudo-boehmite carrier, comprising the steps of:
(1) Modifying kaolin:
adding the modified liquid into a stirring device, and uniformly dispersing the kaolin into the modified liquid to obtain a kaolin dispersion liquid;
performing freeze thawing cycle treatment on the kaolin dispersion liquid for 5-8 times, then performing high-speed centrifugation treatment, standing and filtering to obtain modified filtrate;
(2) Adding urea and a surfactant into the obtained modified filtrate, and stirring at a rotating speed of 150-200r/min for 40-50min to obtain a mixed solution;
(3) Carrying out ultrasonic treatment on the mixed solution to obtain a treated mixed solution;
(4) Dissolving sodium hydroxide in water, adjusting the temperature to 55-60 ℃, and stirring for 20-30min at a constant temperature to prepare sodium hydroxide solution; adding aluminum hydroxide into the obtained sodium hydroxide solution, adjusting the temperature to 75-80 ℃, and stirring for 30-40min at a constant temperature to obtain sodium metaaluminate solution;
(5) Sequentially adding the obtained treatment mixed solution and sodium metaaluminate solution into a reaction kettle, regulating the temperature in the reaction kettle to 75-85 ℃, reacting for 30-40min, then placing the reaction kettle in a centrifugal field for continuous reaction, carrying out two-stage treatment in the centrifugal field, wherein the treatment time in one stage of centrifugal field is 20-30min, the centrifugal rotation speed is 3000-3200r/min, the treatment time in the two stages of centrifugal field is 40-60min, the centrifugal rotation speed is 3500-3800r/min, the treatment interval of the two stages of centrifugal fields is 20-30min, controlling the pH value of a reaction system to be not lower than 9.5 during the reaction, and after the reaction system is separated from the two stages of centrifugal fields, continuing the reaction for 40-50min, ending the reaction, and then filtering to obtain a reactant;
(6) And (3) cleaning the obtained reactant to be neutral by adopting deionized water, filtering, drying in vacuum to constant weight, grinding and sieving to obtain the pseudo-boehmite carrier.
As a further technical scheme: the modified liquid in the step (1) is prepared from the following components in parts by weight:
1-2 parts of maleic anhydride, 6-12 parts of isopropanol, 0.12-0.18 part of rare earth chloride and 60-70 parts of deionized water.
As a further technical scheme: the rare earth chloride is cerium chloride.
As a further technical scheme: the mixing mass ratio of the kaolin to the modifying liquid is 1:12-15.
as a further technical scheme: the freeze thawing cycle treatment is as follows:
firstly, carrying out heat preservation on kaolin dispersion liquid for 10-15 hours at the temperature of minus 25 ℃, and then carrying out heat preservation on the kaolin dispersion liquid for 10-15 hours at the temperature of 25 ℃;
taking 20 hours as a freeze-thawing cycle period, after one freeze-thawing cycle period is finished, sequentially carrying out the next freeze-thawing cycle period, and repeatedly carrying out freeze-thawing cycle treatment on the kaolin dispersion liquid for 5-8 times to finish.
As a further technical scheme: the mixing mass ratio of the modified filtrate, urea and the surfactant in the step (2) is as follows:
20-25:1-3:3-5。
as a further technical scheme: the surfactant is as follows: mixing fatty alcohol polyoxyethylene ether ammonium sulfate with sodium lignin sulfonate;
the mixing mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the sodium lignin sulfonate is 3-4:1-2.
as a further technical scheme: the ultrasonic treatment parameters in the step (3) are as follows:
the ultrasonic treatment time is 10-15min, and the ultrasonic frequency is 35kHz.
As a further technical scheme: the concentration of the sodium hydroxide solution in the step (4) is 1.5-1.8mol/L;
the concentration of the sodium metaaluminate solution in the step (5) is 1.2-1.6mol/L.
As a further technical scheme: the mixing mass ratio of the treatment mixed solution in the step (6) to the sodium metaaluminate solution is 1:3-5.
the pseudo-boehmite prepared by the invention has larger specific surface area, pore volume and good surface acidity, and can be better used as a carrier.
Pseudo-boehmite is a white powder with a space network structure, and has strong dispersibility, good peptization performance, high specific surface and large porosity. Pseudo-boehmite is an important catalyst support material;
according to the invention, the pseudo-boehmite is prepared by mixing the treatment mixed solution and the sodium metaaluminate solution, the particle size of the prepared pseudo-boehmite is reduced, crystal grains generated by the reaction slowly evolve from a spherical shape to a floss spherical aggregate structure, the crystallinity of the pseudo-boehmite gradually increases along with the progress of the reaction, and meanwhile, the specific surface area, the pore volume and the pore diameter of the pseudo-boehmite particles gradually increase, and when the reaction system is lower than 9.5, the specific surface area and the pore volume are obviously reduced, so that the performance of the obtained pseudo-boehmite serving as a carrier is reduced.
The pore size distribution of the prepared pseudo-boehmite can be more concentrated by performing freeze thawing cycle treatment on the kaolin dispersion liquid, so that the pore volume, the specific surface area and the average pore size of the pseudo-boehmite are increased, and the carrying capacity of the pseudo-boehmite carrier is further improved.
When the pseudo-boehmite is prepared conventionally and continuously, complete and incomplete crystal grains which are easy to generate flow out together in the reaction process, incomplete crystal grains are reduced or dissolved due to the change of microenvironment among the particles in the subsequent gel forming reaction, so that the obtained pseudo-boehmite has different crystal grain sizes.
In the conventional preparation process of pseudo-boehmite, microscopic mixing is difficult to be uniform during reaction, reactants and products are mixed together, the nucleation process is easy to be in a non-uniform state, so that the nucleation time is greatly prolonged, meanwhile, the condition of incomplete reaction is easy to occur.
The beneficial effects are that:
the pseudo-boehmite carrier with different pore structures is prepared by the method, and different industrial requirements can be met.
According to the method, the pseudo-boehmite of the pompon-shaped aggregate can be prepared, and the pompon-shaped aggregate has a more complex pore structure, so that the pore volume structure in the pseudo-boehmite is greatly improved, and meanwhile, the heat-resistant stability of the prepared pseudo-boehmite carrier is obviously improved by adopting the treatment mixed liquid prepared from the modified kaolin as a reaction liquid, so that the weather resistance of the pseudo-boehmite is obviously improved. Therefore, the application performance of the pseudo-boehmite prepared by the method is improved, and the pseudo-boehmite prepared by the method can resist impact and pressure in the forming process, can better keep the effect of the original pore structure, and therefore has high pore volume retention rate.
Drawings
FIG. 1 is a graph comparing the effect of different freeze-thaw cycles performed on a kaolin dispersion on pseudo-boehmite pore volume;
FIG. 2 is a graph comparing the effect of different freeze-thaw cycles on heat stability of pseudo-boehmite.
Detailed Description
Example 1
A method for improving weatherability of pseudo-boehmite carrier, comprising the steps of:
(1) Modifying kaolin:
adding the modified liquid into a stirring device, and uniformly dispersing the kaolin into the modified liquid to obtain a kaolin dispersion liquid;
performing freeze thawing cycle treatment on the kaolin dispersion liquid for 5 times, then performing high-speed centrifugal treatment, standing and filtering to obtain modified filtrate;
(2) Adding urea and a surfactant into the obtained modified filtrate, and stirring at a rotating speed of 150r/min for 40min to obtain a mixed solution;
(3) Carrying out ultrasonic treatment on the mixed solution to obtain a treated mixed solution;
(4) Dissolving sodium hydroxide in water, regulating the temperature to 55 ℃, preserving heat and stirring for 20min to prepare sodium hydroxide solution; adding aluminum hydroxide into the obtained sodium hydroxide solution, adjusting the temperature to 75 ℃, and stirring for 30min at a constant temperature to obtain sodium metaaluminate solution;
(5) Sequentially adding the obtained treatment mixed solution and sodium metaaluminate solution into a reaction kettle, regulating the temperature in the reaction kettle to 75 ℃, reacting for 30min, then placing the reaction kettle in a centrifugal field for continuous reaction, carrying out two-stage treatment in the centrifugal field, wherein the treatment time in one-stage centrifugal field is 20min, the centrifugal rotation speed is 3000r/min, the treatment time in the two-stage centrifugal field is 40min, the centrifugal rotation speed is 3500r/min, the treatment interval of the two-stage centrifugal field is 20min, controlling the pH value of a reaction system to be not lower than 9.5 during the reaction, continuing the reaction for 40min after the reaction is separated from the two-stage centrifugal field, ending the reaction, and filtering to obtain a reactant;
(6) And (3) cleaning the obtained reactant to be neutral by adopting deionized water, filtering, drying in vacuum to constant weight, grinding and sieving to obtain the pseudo-boehmite carrier.
The modified liquid in the step (1) is prepared from the following components in parts by weight:
1 part of maleic anhydride, 6 parts of isopropanol, 0.12 part of rare earth chloride and 60 parts of deionized water.
The rare earth chloride is cerium chloride.
The mixing mass ratio of the kaolin to the modifying liquid is 1:12.
the freeze thawing cycle treatment is as follows:
firstly, carrying out heat preservation on kaolin dispersion liquid for 10 hours at the temperature of minus 25 ℃, and then carrying out heat preservation on the kaolin dispersion liquid for 10 hours at the temperature of 25 ℃;
taking 20 hours as a freeze-thawing cycle period, after one freeze-thawing cycle period is finished, sequentially carrying out the next freeze-thawing cycle period, and repeatedly carrying out freeze-thawing cycle treatment on the kaolin dispersion liquid for 5 times to finish.
The mixing mass ratio of the modified filtrate, urea and the surfactant in the step (2) is as follows: 20:1:3.
the surfactant is as follows: mixing fatty alcohol polyoxyethylene ether ammonium sulfate with sodium lignin sulfonate;
the mixing mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the sodium lignin sulfonate is 3:1.
the ultrasonic treatment parameters in the step (3) are as follows:
the time of the ultrasonic treatment was 10min, and the frequency of the ultrasonic wave was 35kHz.
The concentration of the sodium hydroxide solution in the step (4) is 1.5mol/L;
the concentration of the sodium metaaluminate solution in the step (5) is 1.2mol/L.
The mixing mass ratio of the treatment mixed solution in the step (6) to the sodium metaaluminate solution is 1:3.
example 2
A method for improving weatherability of pseudo-boehmite carrier, comprising the steps of:
(1) Modifying kaolin:
adding the modified liquid into a stirring device, and uniformly dispersing the kaolin into the modified liquid to obtain a kaolin dispersion liquid;
performing freeze thawing cycle treatment on the kaolin dispersion liquid for 6 times, then performing high-speed centrifugal treatment, standing and filtering to obtain modified filtrate;
(2) Adding urea and a surfactant into the obtained modified filtrate, and stirring at a rotating speed of 180r/min for 45min to obtain a mixed solution;
(3) Carrying out ultrasonic treatment on the mixed solution to obtain a treated mixed solution;
(4) Dissolving sodium hydroxide in water, regulating the temperature to 57 ℃, preserving heat and stirring for 25min to prepare sodium hydroxide solution; adding aluminum hydroxide into the obtained sodium hydroxide solution, adjusting the temperature to 78 ℃, and stirring for 35min at a constant temperature to obtain sodium metaaluminate solution;
(5) Sequentially adding the obtained treatment mixed solution and sodium metaaluminate solution into a reaction kettle, regulating the temperature in the reaction kettle to 78 ℃, reacting for 35min, then placing the reaction kettle in a centrifugal field for continuous reaction, carrying out two-stage treatment in the centrifugal field, wherein the treatment time in one-stage centrifugal field is 25min, the centrifugal rotation speed is 3100r/min, the treatment time in the two-stage centrifugal field is 50min, the centrifugal rotation speed is 3600r/min, the treatment interval of the two-stage centrifugal field is 25min, controlling the pH value of a reaction system to be not lower than 9.5 during the reaction, continuing the reaction for 45min after the reaction is separated from the two-stage centrifugal field, ending the reaction, and filtering to obtain a reactant;
(6) And (3) cleaning the obtained reactant to be neutral by adopting deionized water, filtering, drying in vacuum to constant weight, grinding and sieving to obtain the pseudo-boehmite carrier.
The modified liquid in the step (1) is prepared from the following components in parts by weight:
1.2 parts of maleic anhydride, 8 parts of isopropanol, 0.14 part of rare earth chloride and 65 parts of deionized water.
The rare earth chloride is cerium chloride.
The mixing mass ratio of the kaolin to the modifying liquid is 1:13.
the freeze thawing cycle treatment is as follows:
firstly, carrying out heat preservation on kaolin dispersion liquid for 12 hours at the temperature of minus 25 ℃, and then carrying out heat preservation on the kaolin dispersion liquid for 12 hours at the temperature of 25 ℃;
taking 20 hours as a freeze-thawing cycle period, after one freeze-thawing cycle period is finished, sequentially carrying out the next freeze-thawing cycle period, and repeatedly carrying out 6 freeze-thawing cycle treatments on the kaolin dispersion liquid to finish.
The mixing mass ratio of the modified filtrate, urea and the surfactant in the step (2) is as follows: 22:2:4.
the surfactant is as follows: mixing fatty alcohol polyoxyethylene ether ammonium sulfate with sodium lignin sulfonate;
the mixing mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the sodium lignin sulfonate is 3.5:1.2.
the ultrasonic treatment parameters in the step (3) are as follows:
the time of the ultrasonic treatment was 12min, and the frequency of the ultrasonic wave was 35kHz.
The concentration of the sodium hydroxide solution in the step (4) is 1.6mol/L;
the concentration of the sodium metaaluminate solution in the step (5) is 1.3mol/L.
The mixing mass ratio of the treatment mixed solution in the step (6) to the sodium metaaluminate solution is 1:3-5.
example 3
A method for improving weatherability of pseudo-boehmite carrier, comprising the steps of:
(1) Modifying kaolin:
adding the modified liquid into a stirring device, and uniformly dispersing the kaolin into the modified liquid to obtain a kaolin dispersion liquid;
performing freeze thawing cycle treatment on the kaolin dispersion liquid for 7 times, then performing high-speed centrifugal treatment, standing and filtering to obtain modified filtrate;
(2) Adding urea and a surfactant into the obtained modified filtrate, and stirring at a rotating speed of 180r/min for 45min to obtain a mixed solution;
(3) Carrying out ultrasonic treatment on the mixed solution to obtain a treated mixed solution;
(4) Dissolving sodium hydroxide in water, regulating the temperature to 56 ℃, preserving heat and stirring for 25min to prepare sodium hydroxide solution; adding aluminum hydroxide into the obtained sodium hydroxide solution, adjusting the temperature to 78 ℃, and stirring for 36min at a constant temperature to obtain sodium metaaluminate solution;
(5) Sequentially adding the obtained treatment mixed solution and sodium metaaluminate solution into a reaction kettle, regulating the temperature in the reaction kettle to 78 ℃, reacting for 35min, then placing the reaction kettle in a centrifugal field for continuous reaction, carrying out two-stage treatment in the centrifugal field, wherein the treatment time in one-stage centrifugal field is 25min, the centrifugal rotation speed is 3150r/min, the treatment time in the two-stage centrifugal field is 50min, the centrifugal rotation speed is 3700r/min, the treatment interval of the two-stage centrifugal field is 25min, controlling the pH value of a reaction system to be not lower than 9.5 during the reaction, continuing the reaction for 45min after the reaction is separated from the two-stage centrifugal field, ending the reaction, and filtering to obtain a reactant;
(6) And (3) cleaning the obtained reactant to be neutral by adopting deionized water, filtering, drying in vacuum to constant weight, grinding and sieving to obtain the pseudo-boehmite carrier.
The modified liquid in the step (1) is prepared from the following components in parts by weight:
1.5 parts of maleic anhydride, 10 parts of isopropanol, 0.16 part of rare earth chloride and 66 parts of deionized water.
The rare earth chloride is cerium chloride.
The mixing mass ratio of the kaolin to the modifying liquid is 1:14.
the freeze thawing cycle treatment is as follows:
firstly, carrying out heat preservation on kaolin dispersion liquid for 14 hours at the temperature of minus 25 ℃, and then carrying out heat preservation on the kaolin dispersion liquid for 14 hours at the temperature of 25 ℃;
taking 20 hours as a freeze-thawing cycle period, after one freeze-thawing cycle period is finished, sequentially carrying out the next freeze-thawing cycle period, and repeatedly carrying out 7 freeze-thawing cycle treatments on the kaolin dispersion liquid to finish.
The mixing mass ratio of the modified filtrate, urea and the surfactant in the step (2) is as follows: 24:2:4.
the surfactant is as follows: mixing fatty alcohol polyoxyethylene ether ammonium sulfate with sodium lignin sulfonate;
the mixing mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the sodium lignin sulfonate is 3.5:1.5.
the ultrasonic treatment parameters in the step (3) are as follows:
the time of the ultrasonic treatment was 12min, and the frequency of the ultrasonic wave was 35kHz.
The concentration of the sodium hydroxide solution in the step (4) is 1.7mol/L;
the concentration of the sodium metaaluminate solution in the step (5) is 1.4mol/L.
The mixing mass ratio of the treatment mixed solution in the step (6) to the sodium metaaluminate solution is 1:4.
example 4
A method for improving weatherability of pseudo-boehmite carrier, comprising the steps of:
(1) Modifying kaolin:
adding the modified liquid into a stirring device, and uniformly dispersing the kaolin into the modified liquid to obtain a kaolin dispersion liquid;
performing freeze thawing cycle treatment on the kaolin dispersion liquid for 8 times, then performing high-speed centrifugal treatment, standing and filtering to obtain modified filtrate;
(2) Adding urea and a surfactant into the obtained modified filtrate, and stirring for 50min at a rotating speed of 200r/min to obtain a mixed solution;
(3) Carrying out ultrasonic treatment on the mixed solution to obtain a treated mixed solution;
(4) Dissolving sodium hydroxide in water, regulating the temperature to 60 ℃, preserving heat and stirring for 30min to prepare sodium hydroxide solution; adding aluminum hydroxide into the obtained sodium hydroxide solution, adjusting the temperature to 80 ℃, and stirring for 40min at a constant temperature to obtain sodium metaaluminate solution;
(5) Sequentially adding the obtained treatment mixed solution and sodium metaaluminate solution into a reaction kettle, regulating the temperature in the reaction kettle to 85 ℃, reacting for 40min, then placing the reaction kettle in a centrifugal field for continuous reaction, carrying out two-stage treatment in the centrifugal field, wherein the treatment time in one-stage centrifugal field is 30min, the centrifugal rotation speed is 3200r/min, the treatment time in the two-stage centrifugal field is 60min, the centrifugal rotation speed is 3800r/min, the treatment interval of the two-stage centrifugal field is 30min, controlling the pH value of a reaction system to be not lower than 9.5 during the reaction, continuing the reaction for 50min after the reaction is separated from the two-stage centrifugal field, ending the reaction, and filtering to obtain a reactant;
(6) And (3) cleaning the obtained reactant to be neutral by adopting deionized water, filtering, drying in vacuum to constant weight, grinding and sieving to obtain the pseudo-boehmite carrier.
The modified liquid in the step (1) is prepared from the following components in parts by weight:
2 parts of maleic anhydride, 12 parts of isopropanol, 0.18 part of rare earth chloride and 70 parts of deionized water.
The rare earth chloride is cerium chloride.
The mixing mass ratio of the kaolin to the modifying liquid is 1:15.
the freeze thawing cycle treatment is as follows:
firstly, carrying out heat preservation on the kaolin dispersion liquid for 15 hours at the temperature of minus 25 ℃, and then carrying out heat preservation on the kaolin dispersion liquid for 15 hours at the temperature of 25 ℃;
taking 20 hours as a freeze-thawing cycle period, after one freeze-thawing cycle period is finished, sequentially carrying out the next freeze-thawing cycle period, and repeatedly carrying out 8 freeze-thawing cycle treatments on the kaolin dispersion liquid to finish.
The mixing mass ratio of the modified filtrate, urea and the surfactant in the step (2) is as follows: 25:3:5.
the surfactant is as follows: mixing fatty alcohol polyoxyethylene ether ammonium sulfate with sodium lignin sulfonate;
the mixing mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the sodium lignin sulfonate is 4:2.
the ultrasonic treatment parameters in the step (3) are as follows:
the time of the ultrasonic treatment was 15min, and the frequency of the ultrasonic wave was 35kHz.
The concentration of the sodium hydroxide solution in the step (4) is 1.8mol/L;
the concentration of the sodium metaaluminate solution in the step (5) is 1.6mol/L.
The mixing mass ratio of the treatment mixed solution in the step (6) to the sodium metaaluminate solution is 1:5.
comparative example 1: the difference from example 1 is the replacement of kaolin with bentonite;
comparative example 2: the difference from example 1 is that the kaolin was not modified;
comparative example 3: the difference from example 1 is that in step (5), the centrifugal field treatment is not performed;
experiment
The particle size distribution of the pseudo-boehmite carrier prepared in the example was examined and the results were as follows:
TABLE 1
As can be seen from Table 1, the pseudo-boehmite carrier prepared by the invention has uniform particle size distribution, and most of the pseudo-boehmite carrier is distributed below 50 mu m.
Abrasion test:
specific surface area measurements were performed on the samples of examples and comparative examples;
TABLE 2
As can be seen from Table 2, the pseudo-boehmite prepared by the invention has a relatively high specific surface area.
Pore volume detection and comparison are carried out on samples of the examples and the comparative examples;
TABLE 3 Table 3
Pore volume/mL/g | |
Example 1 | 0.655 |
Example 2 | 0.660 |
Example 3 | 0.658 |
Example 4 | 0.653 |
Comparative example 1 | 0.496 |
Comparative example 2 | 0.547 |
Comparative example 3 | 0.518 |
As can be seen from Table 3, the pseudo-boehmite prepared by the method has higher pore volume, and the carrying capacity of the pseudo-boehmite carrier is greatly improved through the increase of the pore volume.
Heat resistance test was performed on samples of examples and comparative examples:
taking 30g of each group of samples, weighing, recording, preserving heat for 30min at the temperature of 200 ℃, then weighing again, calculating, and comparing the mass loss rate of each group;
TABLE 4 Table 4
Mass loss rate% | |
Example 1 | 1.32 |
Example 2 | 1.15 |
Example 3 | 1.18 |
Example 4 | 1.26 |
Comparative example 1 | 6.54 |
Comparative example 2 | 4.12 |
Comparative example 3 | 3.98 |
As can be seen from Table 4, the pseudo-boehmite carrier prepared by the invention has better heat resistance and better stability, thereby enhancing the weather resistance.
Based on the sample of example 1, the effect of different freeze-thaw cycles on the kaolin dispersion on the pore volume of pseudo-boehmite was compared as shown in FIG. 1.
Based on the sample of example 1, the effect of different freeze-thaw cycles on the heat stability of pseudo-boehmite is compared as shown in fig. 2.
The foregoing description of the preferred embodiments of the invention should not be taken as limiting the scope of the invention, which is defined by the appended claims, but rather by the description of the preferred embodiments, all changes and modifications that come within the meaning and range of equivalency of the claims are intended to be embraced therein.
Claims (8)
1. A method for improving weather resistance of pseudo-boehmite carrier is characterized in that: the method comprises the following steps:
(1) Modifying kaolin:
adding the modified liquid into a stirring device, and uniformly dispersing the kaolin into the modified liquid to obtain a kaolin dispersion liquid;
performing freeze thawing cycle treatment on the kaolin dispersion liquid for 5-8 times, then performing high-speed centrifugation treatment, standing and filtering to obtain modified filtrate;
(2) Adding urea and a surfactant into the obtained modified filtrate, and stirring at a rotating speed of 150-200r/min for 40-50min to obtain a mixed solution;
(3) Carrying out ultrasonic treatment on the mixed solution to obtain a treated mixed solution;
(4) Dissolving sodium hydroxide in water, adjusting the temperature to 55-60 ℃, and stirring for 20-30min at a constant temperature to prepare sodium hydroxide solution; adding aluminum hydroxide into the obtained sodium hydroxide solution, adjusting the temperature to 75-80 ℃, and stirring for 30-40min at a constant temperature to obtain sodium metaaluminate solution;
(5) Sequentially adding the obtained treatment mixed solution and sodium metaaluminate solution into a reaction kettle, regulating the temperature in the reaction kettle to 75-85 ℃, reacting for 30-40min, then placing the reaction kettle in a centrifugal field for continuous reaction, carrying out two-stage treatment in the centrifugal field, wherein the treatment time in one stage of centrifugal field is 20-30min, the centrifugal rotation speed is 3000-3200r/min, the treatment time in the two stages of centrifugal field is 40-60min, the centrifugal rotation speed is 3500-3800r/min, the treatment interval of the two stages of centrifugal fields is 20-30min, controlling the pH value of a reaction system to be not lower than 9.5 during the reaction, and after the reaction system is separated from the two stages of centrifugal fields, continuing the reaction for 40-50min, ending the reaction, and then filtering to obtain a reactant;
(6) Washing the obtained reactant by deionized water to be neutral, filtering, drying in vacuum to constant weight, grinding and sieving to obtain a pseudo-boehmite carrier;
the modified liquid in the step (1) is prepared from the following components in parts by weight:
1-2 parts of maleic anhydride, 6-12 parts of isopropanol, 0.12-0.18 part of rare earth chloride and 60-70 parts of deionized water;
the freeze thawing cycle treatment is as follows:
firstly, carrying out heat preservation on kaolin dispersion liquid for 10-15 hours at the temperature of minus 25 ℃, and then carrying out heat preservation on the kaolin dispersion liquid for 10-15 hours at the temperature of 25 ℃;
taking 20 hours as a freeze-thawing cycle period, after one freeze-thawing cycle period is finished, sequentially carrying out the next freeze-thawing cycle period, and repeatedly carrying out freeze-thawing cycle treatment on the kaolin dispersion liquid for 5-8 times to finish.
2. The method for improving the weatherability of a pseudo-boehmite carrier according to claim 1, wherein the method comprises the steps of: the rare earth chloride is cerium chloride.
3. The method for improving the weatherability of a pseudo-boehmite carrier according to claim 1, wherein the method comprises the steps of: the mixing mass ratio of the kaolin to the modifying liquid is 1:12-15.
4. The method for improving the weatherability of a pseudo-boehmite carrier according to claim 1, wherein the method comprises the steps of: the mixing mass ratio of the modified filtrate, urea and the surfactant in the step (2) is as follows:
20-25:1-3:3-5。
5. the method for improving the weatherability of a pseudo-boehmite carrier according to claim 1, wherein the method comprises the steps of: the surfactant is as follows: mixing fatty alcohol polyoxyethylene ether ammonium sulfate with sodium lignin sulfonate;
the mixing mass ratio of the fatty alcohol polyoxyethylene ether ammonium sulfate to the sodium lignin sulfonate is 3-4:1-2.
6. The method for improving the weatherability of a pseudo-boehmite carrier according to claim 1, wherein the method comprises the steps of: the ultrasonic treatment parameters in the step (3) are as follows:
the ultrasonic treatment time is 10-15min, and the ultrasonic frequency is 35kHz.
7. The method for improving the weatherability of a pseudo-boehmite carrier according to claim 1, wherein the method comprises the steps of: the concentration of the sodium hydroxide solution in the step (4) is 1.5-1.8mol/L;
the concentration of the sodium metaaluminate solution in the step (5) is 1.2-1.6mol/L.
8. The method for improving the weatherability of a pseudo-boehmite carrier according to claim 1, wherein the method comprises the steps of: the mixing mass ratio of the treatment mixed solution in the step (6) to the sodium metaaluminate solution is 1:3-5.
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