CN114042443B - Forming method of spherical alumina - Google Patents

Forming method of spherical alumina Download PDF

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CN114042443B
CN114042443B CN202111428390.9A CN202111428390A CN114042443B CN 114042443 B CN114042443 B CN 114042443B CN 202111428390 A CN202111428390 A CN 202111428390A CN 114042443 B CN114042443 B CN 114042443B
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aluminum hydroxide
alginate
boehmite
pseudo
acid
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CN114042443A (en
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魏小波
武亚梅
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • 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
    • C01F7/021—After-treatment of oxides or hydroxides
    • C01F7/025—Granulation or agglomeration

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  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention belongs to the technical field of catalyst carriers, and particularly discloses a forming method of spherical alumina, which comprises the steps of mixing boehmite, pseudo-boehmite or a mixture of boehmite and pseudo-boehmite with water to prepare aluminum hydroxide slurry, adding acid into the aluminum hydroxide slurry to acidify aluminum hydroxide to form acidified aluminum hydroxide slurry, adding urea and a proper amount of pseudo-boehmite, solid oxide or molecular sieve into the acidified aluminum hydroxide slurry, stirring uniformly to form aluminum hydroxide sol, dripping the obtained aluminum hydroxide sol into an oil ammonia column to form spherical gel particles, aging the gel particles in an alginate solution phase, separating gel balls, drying and roasting to obtain spherical hydrated alumina particles, maintaining excellent pore structure and large specific surface area of the pseudo-boehmite, and having high hydrothermal stability, thus having wide application prospect.

Description

Forming method of spherical alumina
Technical Field
The invention belongs to the technical field of catalyst carriers, and particularly discloses a forming method of spherical alumina.
Background
The oil ammonia column forming process is one common process of preparing alumina, silica-alumina and other small balls, and through dropping sol into the oil ammonia column to form sol particle into ball in the upper oil phase of the column, gelatinizing in the lower ammonia water layer, ageing the gelatinized particle, drying and roasting to obtain spherical solid particle.
Alginic acid is a natural biological material with sol-gel property, is widely used for preparing materials such as microcapsule, hydrogel, etc., a method for preparing spherical alumina particles by using alginic acid assisted molding method is recently proposed, and the preparation of spherical particles is carried out in water columns by utilizing the rapid sol-gel property of alginic acid and the embedding property of three-dimensional network structure when gel is formed.
The alginic acid auxiliary forming method is a water column forming method, and has high forming efficiency and low cost, but because the bonding modes of alginic acid and different metal cations are different, and the surface tension of ionic salt solution is also different, the sphericity of gel particles in forming is greatly different. The sphericity of the product is good when the product is molded in calcium and zinc ion solution, but more impurity ions are introduced, so that the product is unfavorable for preparing high-purity alumina; meanwhile, because pseudo-boehmite only forms a suspension liquid in a physical state in an alginate solution, the specific surface area, pore volume and pore distribution of the pellets are limited in adjusting capacity in the subsequent treatment process during molding, the method cannot adapt to the adjustment and change of the properties of the pellets to a greater extent, and the structural properties, purity and sphericity of the product cannot be considered by adopting the method.
The aqueous phase of the oil ammonia column method is ammonia water, and the acidity of the aluminum sol is neutralized by the ammonia water, so that the aluminum sol is gelled, but the ammonia water volatilizes in the use process to cause environmental pollution, the strength of the sol drops after being gelled in the ammonia water is very low, and the next drying treatment can be performed after the curing degree of the sol drops is increased by long-time aging treatment, so that the preparation time is long and the efficiency is low.
Disclosure of Invention
In order to solve the problems in the background technology, the invention discloses a forming method of spherical alumina, which utilizes an oil ammonia column method to prepare the spherical alumina, and solves the problems of long aging time, low efficiency, hydrothermal stability and the like of the oil ammonia column in the background of the prior art, and the problems that the structural property, purity and sphericity of the product of the alginic acid auxiliary forming method cannot be considered.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for forming spherical alumina, comprising the steps of:
(1) Preparing aluminum sol: mixing boehmite, pseudo-boehmite or a mixture of boehmite and pseudo-boehmite with water to prepare aluminum hydroxide slurry, adding acid into the aluminum hydroxide slurry to acidify the aluminum hydroxide to form acidified aluminum hydroxide slurry, adding urea and a proper amount of pseudo-boehmite, solid oxide or molecular sieve into the acidified aluminum hydroxide slurry, and uniformly stirring to form aluminum hydroxide sol with the solid content of 10-30 mass% calculated by alumina;
(2) Dissolving soluble alginate in water, stirring to obtain transparent alginate solution with viscosity, wherein the content of alginate in the solution alginate is 0.5-2 wt%, adding ammonia water into the ammonium alginate solution, stirring uniformly to obtain an ammonium alginate ammonia solution, and preparing an oil ammonia column consisting of an upper oil phase with the thickness of 0.5-15 mm and a lower soluble alginate solution phase with the thickness of 20-500 cm by using the ammonium alginate ammonia solution and the oil phase;
(3) And (3) dripping the aluminum hydroxide sol obtained in the step (1) into the oil ammonia column obtained in the step (2) to form spherical gel particles, then aging the gel particles in an alginate solution phase for 0.1-20 hours, separating gel balls after aging, drying and roasting to obtain spherical hydrated alumina particles.
Further, the temperature of the soluble alginate solution phase in the oil ammonia column of step (2) is between 35 and 55 ℃.
Further, the acid in step (1) is nitric acid, oxalic acid, hydrochloric acid, perchloric acid, formic acid or acetic acid.
Further, the acid in the step (1) is nitric acid having a concentration of 5 to 50 mass%.
Further, the soluble alginate in the step (2) is one or more of sodium alginate, potassium alginate, magnesium alginate and ammonium alginate.
Further, the alginate content in the alginate solution is 0.7-2 wt%.
Further, the oil phase is C 8 -C 20 One or two or more of alkane, straight-run gasoline and kerosene.
Further, the oil phase is one or two or more of octane, liquid paraffin, straight-run gasoline and kerosene.
Further, the pseudo-boehmite, the solid oxide or the molecular sieve added to the acidified aluminum hydroxide slurry in step (1) is present in an amount of between 0 and 60 mass%.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts pseudo-boehmite as raw material, one part of pseudo-boehmite is made into sol after acidification peptization, the other part of pseudo-boehmite, molecular sieve or solid oxide is dispersed in deionized water to prepare suspension, the two are mixed to prepare pseudo-boehmite forming solution with certain viscosity, and the spherical gamma-AI is prepared after the oil ammonia column forming, aging, washing, drying and roasting 2 0 3 The carrier, because part of pseudo-boehmite is not peptized, makes the prepared spherical gamma-AI 2 0 3 Is spherical gamma-Al containing molecular sieve 2 0 3 The pore structure and the large specific surface area of the pseudo-boehmite are maintained, the pseudo-boehmite has high hydrothermal stability, can be used in the platinum reforming catalytic carrier and other catalytic fields, and has wide application prospect.
The method combines the advantages of an oil ammonia column method and an alginic acid auxiliary method, has the advantages of high forming speed, high efficiency, high product strength, good sphericity, capability of continuously adjusting the strength of the pellets in an aging period, large grain size range, no pollution in the preparation process and the like, and is simple and feasible in operation steps.
Detailed Description
Example 1
(1) Preparation of aluminum sol
Taking 8 g of aluminum hydroxide powder with the trade name of SB and produced by Sasol company in Germany, adding 18 ml of deionized water, stirring for half an hour to moisten and pulpify, adding 6g of 6% nitric acid solution and 6g of acidified hydroxide slurry, adding 3g of urea under stirring, and uniformly stirring for later use;
(2) 100 g of ammonium alginate is dissolved in 714ml of deionized water under stirring for 2-6 hours to obtain transparent solution with certain viscosity, wherein the content of the ammonium alginate in the solution is 1 wt%; adding 286 g of 28% concentrated ammonia water into the mixture, uniformly stirring the mixture for later use, adding the prepared ammonia water solution of ammonium alginate into a drop ball forming tube of an oil ammonia column forming device, wherein the column height is 80 cm, adding liquid paraffin with the thickness of 3 mm into the upper part of the oil ammonia column forming device, forming an ammonia water solution of ammonium alginate with the concentration of 8 mass% into the lower part of the oil ammonia column forming device, and heating and preserving the temperature of the solution to 40 ℃;
(3) Drop ball forming: pouring the alumina sol prepared in the step (1) into a ball dropping device above an oil ammonia column, wherein the needle hole at the bottom of the ball dropping device is 3cm away from the oil surface of the oil ammonia column obtained in the step (2), the ball dropping speed is controlled at 30 drops/min, aging for 0.2-10h at about 40 ℃, separating gel balls after aging is finished, drying the gel balls to constant weight at 80 ℃ to obtain spherical hydrated alumina particles, and roasting the small spherical particles at 600 ℃ for 4h to obtain gamma-AI 2 0 3 A carrier A having a specific surface area of 189m 2 Per gram, 0.98ml/g pore volume, 120 angstrom in diameter, 0.62g/ml bulk density and 69 newtons/grain crush strength.
The oil ammonia column forming device used here has a glass column length of 1.0m and a diameter of 30mm, the upper middle end of the glass column is provided with an overflow port, the overflow port is connected with a container for recovering overflowed solution, the lower end is provided with a plug valve, the lower end is connected with a container for receiving gel pellets, and the plug valve is used for separating the gel pellets.
Example 2
Preparation of gamma-AI according to example 1 2 0 3 A pellet support, except that tin dioxide powder of 0.024 g was added to the acidified aluminum hydroxide slurry to make a tin dioxide containing slurryAnd a small amount of tin ion, wherein tin dioxide is added so that the Sn content in the alumina is 0.40 mass%, and the above sol is formed into a droplet in the same manner as in step (3) of example 1 to obtain Sn-containing gamma-Al 2 O 3 A carrier B having a specific surface area of 183m 2 Per gram, 0.73ml/g pore volume, 96 angstrom in diameter, 0.63g/ml bulk density and 58 newtons/particle crush strength.
Example 3
Preparation of gamma-Al according to the procedure of example 1 2 0 3 The pellet carrier was prepared by adding 9g of ZSM-5 molecular sieve powder to the acidified aluminum hydroxide slurry to prepare a ZSM-5 molecular sieve-containing sol, adding the molecular sieve so that the molecular sieve content in the prepared alumina was 60 mass%, and drop-forming the sol in the same manner as in step (3) of example 1 to obtain ZSM-5-containing gamma-Al 2 O 3 A carrier C having a specific surface area of 255m 2 Per gram, pore volume 0.67ml/g, several pore diameters of 83 angstroms, bulk density 0.89g/ml, crush strength 39 newtons/grain.
Example 4
Preparation of gamma-Al according to the procedure of example 1 2 0 3 The pellet carrier was prepared by adding 4 g of ZSM-5 molecular sieve powder to the acidified aluminum hydroxide slurry to prepare a ZSM-5 molecular sieve-containing sol, adding the molecular sieve so that the molecular sieve content in the prepared alumina was 40% by mass, and drop-forming the sol by the method of step (3) of example 1 to prepare ZSM-5-containing gamma-Al 2 O 3 A carrier D having a specific surface area of 234m 2 Per gram, 0.65ml/g pore volume, 77 angstrom in diameter, 0.79g/ml bulk density and 46 newton/grain crush strength.
Example 5
(1) Preparation of aluminum sol
Taking 16 g of aluminum hydroxide powder with the trade name of SB and produced by Sasol company in Germany, adding 36 ml of deionized water, stirring for half an hour to moisten and pulpify, adding 12 g of 6% nitric acid solution, acidifying the aluminum hydroxide powder, adding 6g of urea under stirring, adding 7 g of ZSM-5 molecular sieve powder into the acidified aluminum hydroxide slurry to prepare sol containing ZSM-5 molecular sieve, and uniformly stirring the added molecular sieve to make the molecular sieve content in the prepared alumina be 5 mass percent for later use;
(2) Dissolving 2g of potassium alginate in 714ml of deionized water under stirring for 2-6 hours to obtain a transparent solution with certain viscosity, wherein the content of the potassium alginate in the solution is 2 wt%; adding 286 g of 28% concentrated ammonia water, uniformly stirring for later use, adding the prepared ammonia water solution of potassium alginate into a drop ball forming tube of an oil ammonia column forming device, wherein the column height is 100 cm, adding 15 mm thick liquid paraffin into the upper part to form potassium alginate solution of ammonia water with the concentration of 8 mass% in the lower part, and heating and preserving the temperature of the solution to 55 ℃;
(3) Shaping the aluminum sol prepared in the step (1) by using an oil ammonia column shaping device in the step (2), controlling the needle hole at the bottom of a dripper to be 2cm away from the oil surface, controlling the speed of dripping balls to be 50 drops/min, aging at about 40-55 ℃ for 0.2-10h, separating gel balls after aging, drying the gel balls to constant weight at 80 ℃ to obtain spherical hydrated alumina particles, and roasting the small spherical particles at 600 ℃ for 4h to obtain gamma-Al containing a small amount of potassium and 5% ZSM-5 molecular sieve 2 0 3 A carrier E having a specific surface area of 212m 2 Per gram, a pore volume of 0.84ml/g, a few pores diameter of 86 angstroms, a bulk density of 0.72g/ml and a crush strength of 59 newtons/grain.
Example 6
Preparation of gamma-Al according to the procedure of example 5 2 0 3 The pellet carrier was prepared by adding 0.1 g of tin dioxide powder to the acidified aluminum hydroxide slurry to prepare a sol containing tin dioxide and a small amount of tin ions, adding tin dioxide so that the Sn content in the prepared alumina was 0.78 mass%, drop-forming the sol in the manner of step (3) of example 1 to prepare a potassium alginate solution having a concentration of 0.7%, adding 7 mm thick liquid paraffin to the upper inner part of a drop-forming tube during dropping, and obtaining gamma-Al having a column height of 200 cm and 0.78% Sn 2 O 3 A carrier F having a specific surface area of 190m 2 Per gram, a pore volume of 0.913ml/g, a few pores diameter of 97 angstroms, a bulk density of 0.62g/ml and a crush strength of 65 newtons/grain.
Example 7
According to the embodiment5 preparation of gamma-Al 2 0 3 The pellet support was prepared by adding 4 g of the SAPO-34 molecular sieve powder to the acidified aluminum hydroxide slurry to prepare a SAPO-34 molecular sieve-containing sol, dropping the sol into pellets in the same manner as in example 1 (3) to obtain a column height of 500 cm, thereby obtaining SAPO-34-containing gamma-Al 2 O 3 A carrier H having a specific surface area of 208m 2 Per gram, pore volume 0.69ml/g, several pore diameters 88 angstrom, bulk density 0.76g/ml, crush strength 48 newtons/grain.
Example 8
Preparation of gamma-Al according to the procedure of example 5 2 0 3 The pellet support was prepared by adding 3.5 g of a high-fineness silver oxide powder to an acidified aluminum hydroxide slurry to prepare a silver oxide-containing sol, adding silver oxide so that the silver oxide content in the prepared alumina was 17% by mass, and drop-molding the sol in the same manner as in step (3) of example 1 to obtain a silver oxide-containing gamma-Al 2 O 3 A carrier I having a specific surface area of 198m 2 Per gram, pore volume 0.86ml/g, pore diameter 101 angstrom, bulk density 0.71g/ml, crush strength 52 newtons/grain.
Prepared spherical gamma-Al 2 0 3 Or spherical gamma-Al containing molecular sieve 2 0 3 The pore structure and the large specific surface area of the pseudo-boehmite are maintained, the pseudo-boehmite has high hydrothermal stability, can be used in the platinum reforming catalytic carrier and other catalytic fields, and has wide application prospect.

Claims (8)

1. The forming method of the spherical alumina is characterized by comprising the following steps of:
(1) Preparing aluminum sol: mixing boehmite, pseudo-boehmite or a mixture of boehmite and pseudo-boehmite with water to prepare aluminum hydroxide slurry, adding acid into the aluminum hydroxide slurry to acidify the aluminum hydroxide to form acidified aluminum hydroxide slurry, adding urea and a proper amount of pseudo-boehmite, solid oxide or molecular sieve into the acidified aluminum hydroxide slurry, and uniformly stirring to form aluminum hydroxide sol with the solid content of 10-30 mass% calculated by alumina;
(2) Dissolving soluble alginate in water, stirring to obtain transparent alginate solution with viscosity, wherein the content of alginate in the solution alginate is 0.5-2 wt%, adding ammonia water into the ammonium alginate solution, stirring uniformly to obtain an ammonium alginate ammonia solution, and preparing an oil ammonia column consisting of an upper oil phase with the thickness of 0.5-15 mm and a lower soluble alginate solution phase with the thickness of 20-500 cm by utilizing the ammonium alginate ammonia solution and the oil phase;
(3) And (3) dripping the aluminum hydroxide sol obtained in the step (1) into the oil ammonia column obtained in the step (2) to form spherical gel particles, then aging the gel particles in an alginate solution phase for 0.1-20 hours, separating gel balls after aging, drying and roasting to obtain spherical hydrated alumina particles.
2. The method of forming spherical alumina according to claim 1, wherein the temperature of the soluble alginate solution phase in the oil ammonia column of step (2) is between 35-55 ℃.
3. The method of forming spherical alumina according to claim 2, wherein the acid in step (1) is nitric acid, oxalic acid, hydrochloric acid, perchloric acid, formic acid or acetic acid.
4. The method for molding spherical alumina according to claim 2, wherein the acid in the step (1) is nitric acid having a concentration of 5 to 50 mass%.
5. The method of forming spherical alumina according to claim 2, wherein the soluble alginate in step (2) is one or more of sodium alginate, potassium alginate, magnesium alginate, and ammonium alginate.
6. A method of forming spherical alumina according to claim 2, wherein the alginate content of the alginate solution is 0.7-2% by weight.
7. The method for forming spherical alumina according to claim 2, wherein the oil phase is C 8 -C 20 One or two or more of alkane, straight-run gasoline and kerosene.
8. The method for forming spherical alumina according to claim 2, wherein the oil phase is one or two or more of octane, liquid paraffin, straight-run gasoline, kerosene.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104402028A (en) * 2014-11-12 2015-03-11 中国海洋石油总公司 Forming method for spherical aluminium oxide through oil-water column process
CN104477953A (en) * 2014-11-12 2015-04-01 中国海洋石油总公司 Spherical alumina shaping method
CN104891538A (en) * 2015-04-30 2015-09-09 北京化工大学 Hydrothermally-stable spherical gamma-Al2O3 and preparation method thereof
CN111482203A (en) * 2019-01-25 2020-08-04 上海杰标能源科技有限公司 Method for molding hollow spherical carrier
CN112973771A (en) * 2021-02-25 2021-06-18 西南化工研究设计院有限公司 Spherical catalyst carrier containing molecular sieve and alumina, preparation and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104402028A (en) * 2014-11-12 2015-03-11 中国海洋石油总公司 Forming method for spherical aluminium oxide through oil-water column process
CN104477953A (en) * 2014-11-12 2015-04-01 中国海洋石油总公司 Spherical alumina shaping method
CN104891538A (en) * 2015-04-30 2015-09-09 北京化工大学 Hydrothermally-stable spherical gamma-Al2O3 and preparation method thereof
CN111482203A (en) * 2019-01-25 2020-08-04 上海杰标能源科技有限公司 Method for molding hollow spherical carrier
CN112973771A (en) * 2021-02-25 2021-06-18 西南化工研究设计院有限公司 Spherical catalyst carrier containing molecular sieve and alumina, preparation and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A New Strategy in the Synthesis of Hollow gamma-Al2O3 Nanosphere using Alginate Gel Casting Process;Sadjadi, MS、Rostamizadeh, N;《RESEARCH JOURNAL OF BIOTECHNOLOGY》;30-35 *
海藻酸钠凝胶–发泡法制备Al2O3多孔陶瓷;何秀兰等;《硅酸盐学报》;368-374 *
顾其胜等.《海藻酸盐基生物医用材料与临床医学》.上海科学技术出版社,2015,215. *

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