CN114644352B - Double-pore distribution alumina spherical particle and preparation method thereof - Google Patents

Double-pore distribution alumina spherical particle and preparation method thereof Download PDF

Info

Publication number
CN114644352B
CN114644352B CN202011493267.0A CN202011493267A CN114644352B CN 114644352 B CN114644352 B CN 114644352B CN 202011493267 A CN202011493267 A CN 202011493267A CN 114644352 B CN114644352 B CN 114644352B
Authority
CN
China
Prior art keywords
aging
starch
pore
double
spherical particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011493267.0A
Other languages
Chinese (zh)
Other versions
CN114644352A (en
Inventor
杨卫亚
王刚
隋宝宽
袁胜华
王少军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Dalian Petrochemical Research Institute Co ltd, China Petroleum and Chemical Corp filed Critical Sinopec Dalian Petrochemical Research Institute Co ltd
Priority to CN202011493267.0A priority Critical patent/CN114644352B/en
Publication of CN114644352A publication Critical patent/CN114644352A/en
Application granted granted Critical
Publication of CN114644352B publication Critical patent/CN114644352B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • 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
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • 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
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C01F7/308—Thermal decomposition of nitrates
    • 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
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C01F7/32—Thermal decomposition of sulfates including complex sulfates, e.g. alums
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • 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
    • C01P2006/21—Attrition-index or crushing strength of granulates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Catalysts (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention discloses a double-pore distribution alumina spherical particle and a preparation method thereof. Has the following properties: spherical particles with the diameter of 0.5-1.5mm, the mesoporous size range of 10-30nm, the pore volume ratio of 30-70%, the macroporous size distribution of 100-400nm, the pore volume ratio of 20-60%, the crushing strength of 50-100N/particle and the abrasion rate of not more than 0.5wt%. The preparation method comprises the following steps: (1) Uniformly mixing water, low-carbon alcohol, inorganic aluminum salt, starch and sesbania powder, heating to 50-60 ℃, and then adding alkylene oxide to form a uniform mixture a; (2) And (3) dripping the mixture a obtained in the step (1) into melted Vaseline to form gel balls, performing first aging and washing on the gel balls in the Vaseline, performing second aging in an alkaline aqueous solution, and performing washing, drying and roasting on the gel balls after the second aging to obtain a product. The double-pore distribution alumina spherical particles have mesoporous-large Kong Shuangchong pore distribution, large pores are communicated in three dimensions, the crushing strength is high, the abrasion rate is low, and the double-pore distribution alumina spherical particles can be used as a good carrier of a catalyst.

Description

Double-pore distribution alumina spherical particle and preparation method thereof
Technical Field
The invention belongs to the field of inorganic material preparation, and relates to a double-pore distribution alumina spherical particle and a preparation method thereof.
Background
Spherical alumina particles are widely used in the fields of catalysts, catalyst carriers, adsorption separation materials and the like. CN201610296618.6 uses starch, cereal flour, latex, polystyrene, acrylic particles, polysaccharide, carbon black particles, solid pore-forming agent of sawdust and pore-forming agent of hydrocarbon liquid as templates, and is mixed with water, acid and at least one suspension of boehmite powder, and the mixture is formed into spheres after being dripped, and then the spheres are dried and baked, and the gas generated by decomposing the pore-forming agent is utilized to form macroporous channels. The macropores obtained by the method have strong randomness, and are difficult to form three-dimensional through macropore tunnels. CN201110116418.5 is formed by oil column to obtain mesoporous-rich spherical alumina. CN200710178804.0 adopts a heavy oil residue emulsion template method to synthesize a macroporous carrier, and the obtained macropores are non-penetrating capsule holes. CN111517347a, mixing and stirring pseudo-boehmite with water, acid and urea, and shaping with oil ammonia column to obtain spherical alumina. CN101200297a discloses a method for preparing monolithic macroporous alumina, the obtained product is easily broken into small particles with different shapes and sizes. CN201010221297.6 regulates the formation of macropores and the aperture thereof by using polyethylene glycol, and can obtain macropores of 50-10000nm, but the obtained macropores are isolated and have poor space consistency, the prepared material still has no fixed shape in appearance, and the high molecular weight polyethylene glycol pore-forming agent has high price and is unfavorable for reducing the cost. The spherical alumina prepared by adopting the oil column molding in CN103055950A has low wear resistance, and is easy to fall off powder and block a reactor bed layer when being used for certain heterogeneous catalytic system particles.
For the catalytic reaction of macromolecules such as heavy oil, besides normal active pores, the carrier or the catalyst is generally required to have three-dimensional through macroporous channels so as to reduce the diffusion resistance of the macromolecules, thereby improving the carbon deposition resistance and impurity metal containing capacity of the catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a double-pore distribution alumina spherical particle and a preparation method thereof. The double-pore distribution alumina spherical particles have mesoporous-macroporous Kong Shuangchong pore distribution, large pores are three-dimensionally communicated, have high crushing strength and low abrasion rate, can meet the severe requirements of heterogeneous catalytic reaction under various conditions, and can be used as a good carrier of a catalyst.
The double-pore distribution alumina spherical particles have the following properties: spherical particles with diameter of 0.5-1.5mm, mesoporous size range of 10-30nm, pore volume ratio of 30-70%, macroporous size distribution of 100-400nm, pore volume ratio of 20-60%, crushing strength of 50-100N/granule, abrasion rate of not more than 0.5wt%, BET specific surface area of 150-350m 2 Per g, pore volume of 0.5-1.0cm 3 /g。
The preparation method of the double-pore distribution alumina spherical particles comprises the following steps:
(1) Uniformly mixing water, low-carbon alcohol, inorganic aluminum salt, starch and sesbania gum, heating to 50-60 ℃, and then adding alkylene oxide to form a uniform mixture a;
(2) And (3) dripping the mixture a obtained in the step (1) into melted Vaseline to form gel balls, performing first aging and washing on the gel balls in the Vaseline, performing second aging in an alkaline aqueous solution, and performing washing, drying and roasting on the gel balls after the second aging to obtain a product.
In the method of the present invention, the lower alcohol in the step (1) is a monohydric alcohol having no more than 5 carbon atoms, preferably methanol and/or ethanol.
In the method of the invention, the inorganic aluminum salt in the step (1) is one or more of aluminum nitrate, aluminum chloride or aluminum sulfate.
In the method of the invention, the starch in the step (1) is one or more of corn starch, wheat starch, sweet potato starch, lotus root starch or potato starch.
In the method of the invention, the alkylene oxide in the step (1) is one or more of propylene oxide, butylene oxide or isomers with the same carbon number as the alkylene.
In the method, the weight of the mixture a obtained in the step (1) is taken as a reference, water is 20-35%, low carbon alcohol is 15-35%, inorganic aluminum salt is 15-35%, starch is 1-5%, sesbania gum powder is 1-5%, and alkylene oxide is 10-35%.
In the method of the invention, the melted vaseline in the step (2) is in a liquid state, and the temperature is generally 60-90 ℃.
In the method of the invention, the first aging condition in the step (2) is as follows: aging at 60-90deg.C for 12-48 hr.
In the method of the present invention, after the aging in the step (2), the gel balls are separated, usually by filtration, wherein the gel balls are washed after the first aging, and the vaseline can be eluted by using a solvent capable of dissolving the vaseline, such as acetone, gasoline, benzene, toluene, etc. The gel balls after primary aging can be burnt out by a heating mode of a subsequent drying and roasting stage without solvent washing.
In the method, the second aging in the step (2) is carried out in a closed container, the aging time is 1-12 hours, the temperature is 100-200 ℃, and the pressure is the autogenous pressure of the closed container. The alkaline aqueous solution is ammonium bicarbonate or urea aqueous solution, the mass percentage concentration is 5-30%, and the dosage of the alkaline aqueous solution at least meets the requirement of completely submerging the treated gel balls.
In the method, the washing after the second aging in the step (2) is performed by water until the washing liquid is neutral or nearly neutral.
In the method of the present invention, the drying conditions in step (2) are as follows: the drying temperature is 100-200deg.C, and the drying time is 12-24 hours. The roasting conditions are as follows: roasting temperature is 500-750 ℃ and roasting time is 1-12 hours. The above overdrying and firing processes are performed under an air or oxygen atmosphere.
By adopting the preparation method of the spherical alumina, the alumina spherical particles with high specific surface, large-pore three-dimensional penetration, high crushing strength and low abrasion rate and double-pore distribution can be obtained. The starch and sesbania powder used in the invention are mixed with other materials to be swelled and hydrolyzed to form sol, the sol and alumina precursor are jointly converted into gel after being dripped, in the primary aging process, the starch, the sesbania powder and the gel are separated to be separated out from the gel, and the occupied three-dimensional network space structure is formed into three-dimensional through macropores after washing or burning. The starch and sesbania powder adopted by the invention have low price, and can obviously reduce the product cost. The obtained product can be used as a carrier of a heterogeneous catalyst, such as residual oil hydrogenation reaction, alkylation reaction, and adsorption and degradation of pollutants in the water treatment process.
Drawings
Fig. 1 is an optical camera photograph of the spherical alumina particles prepared in example 1.
Fig. 2 is a scanning electron microscope image of the spherical alumina particles prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples. In the invention, the diameter of spherical particles is measured by a vernier caliper, the three-dimensional penetrability of macropores of a sample is observed by a scanning electron microscope, the mechanical strength is tested by adopting a DL3 type intensity meter, the specific surface area is tested by adopting a BET method, the abrasion rate is tested according to the method described in HG/T3927-2007, and the pore volume is tested by a mercury intrusion method, the pore canal size and the pore distribution, wherein the pore volume ratio is the contribution of pores with a certain size range to the whole pore volume.
Example 1
Mixing water, ethanol, corn starch, sesbania powder and aluminum nitrate at room temperature, heating to 50deg.C to form uniform jelly, adding propylene oxide, and stirring. The water, the ethanol, the corn starch, the sesbania powder gum, the aluminum nitrate and the propylene oxide are respectively and uniformly mixed with the mass contents of 23%, 27%, 2%, 3%, 20% and 25%. Dropping the mixture into liquid vaseline at 60 deg.c with dispersing dripper, maintaining the mixture in the vaseline for 15 hr to age, filtering out the aged gel ball, washing residual vaseline with acetone, soaking in 20wt% concentration ammonium bicarbonate solution, ageing at 140 deg.c for 5 hr, washing with water, stoving at 120 deg.c for 12 hr and roasting at 550 deg.c for 3 hr to obtain final sample.
The product obtained was spherical particles of uniform size with an average diameter of 0.9mm. The product is observed by a scanning electron microscope to show three-dimensional through macroporous channels on the section or the surface of the particles. The crushing strength was 65N/particle, the attrition rate was 0.41% by weight, and the BET specific surface area was 263m 2 Per g, pore volume of 0.68cm 3 And/g. The mesoporous-macroporous composite material has mesoporous-macroporous Kong Shuangchong pore distribution, wherein the mesoporous size distribution is 10-19nm, the pore volume ratio is 51%, the macroporous size distribution is 100-300nm, and the pore volume ratio is 38%.
Example 2
Mixing water, ethanol, sweet potato starch, sesbania powder and aluminum chloride at room temperature, heating to 55deg.C to form uniform jelly, adding butylene oxide, and stirring. The water, the ethanol, the sweet potato starch, the sesbania powder gum, the aluminum chloride and the epoxybutane are respectively mixed evenly with the mass contents of 25 percent, 20 percent, 3 percent, 2 percent, 30 percent and 20 percent. Dropping the mixture into liquid vaseline at 70 ℃ by using a dispersing dropping head, continuously aging in the vaseline for 12 hours after balling, filtering out the aged gel balls, washing residual vaseline with gasoline, immersing in a 25wt% urea solution, aging for 12 hours at 180 ℃ under autogenous pressure, washing with water, drying for 12 hours at 120 ℃, and roasting for 3 hours at 650 ℃ to obtain a final sample.
The product obtained was spherical particles of uniform size with an average diameter of 0.8mm. The product is observed by a scanning electron microscope to show three-dimensional through macroporous channels on the section or the surface of the particles. The crushing strength was 61N/particle, the attrition rate was 0.43wt%, and the BET specific surface area was 249m 2 Per g, pore volume of 0.71cm 3 And/g. Has mesoporous-large Kong Shuangchong pore distribution, wherein the mesoporous size distribution is 12-25nm, the pore volume ratio is 49%, the macroporous size distribution is 100-270nm, and the pore volume ratio is41%。
Example 3
Mixing water, ethanol, potato starch, sesbania powder and aluminum sulfate at room temperature, heating to 60deg.C to obtain uniform jelly, adding propylene oxide, and stirring. The water, the methanol, the potato starch, the sesbania powder gum, the aluminum sulfate and the propylene oxide are respectively mixed uniformly in the mass content of 30%, 20%, 5%, 20% and 20%. Dropping the mixture into liquid vaseline at 90 deg.c with dispersing dripper, maintaining the mixture in the vaseline for 12 hr to age, filtering out the aged gel ball, washing residual vaseline with gasoline, soaking in 25wt% concentration ammonium bicarbonate solution, ageing at 200 deg.c for 12 hr, washing with water, stoving at 120 deg.c for 12 hr and roasting at 550 deg.c for 3 hr to obtain the final sample.
The product obtained was spherical particles of uniform size with an average diameter of 1.8mm. The product is observed by a scanning electron microscope to show three-dimensional through macroporous channels on the section or the surface of the particles. The crushing strength was 76N/particle, the attrition rate was 0.45wt%, and the BET specific surface area was 279m 2 Per g, pore volume of 0.91cm 3 And/g. The porous ceramic material has mesoporous-large Kong Shuangchong pore distribution, wherein the mesoporous size distribution is 10-30nm, the pore volume ratio is 56%, the macroporous size distribution is 150-350nm, and the pore volume ratio is 41%.
Example 4
Samples were prepared as in example 1, except that starch and sesbania powder were not added. The obtained result is observed by a scanning electron microscope, and no obvious three-dimensional macropores exist on the surface and the section.
Example 5
Samples were prepared as in example 1, except that sesbania powder was replaced with starch. The results obtained were observed by a scanning electron microscope, and the surface and the section were similar to those of example 1, but the crush strength was 62N/particle.
Example 6
Samples were prepared as in example 1, except that after dropping the pellets in step (2), they were not subjected to secondary aging, but were directly dried and calcined. The morphology of the resulting samples was similar to the examples, but the crush strength was 58N/particle.
Comparative example 1
Spherical alumina particles were prepared according to the method provided in CN201910759153.7, and the resulting product had higher strength, but it was observed that the sample particles did not have a distinct three-dimensional macroporous structure.
Comparative example 2
The spherical alumina having three-dimensional through macropores and higher crush strength was obtained according to the method of example 1 of CN103055950a, and the abrasion rate of the sample reached 1.7wt% under the same firing conditions as in example 1 of the present invention, and powder falling was easy.
Comparative example 3
Macroporous alumina was prepared as in example 1 of CN101200297a, and the resulting product particles were friable and in irregular small pieces.
Comparative example 4
Materials were prepared according to the method of CN201610296618.6 example 2. The obtained product is observed by a scanning electron microscope, the appearance of the surface and the section is provided with dispersed macropores, and the three-dimensional penetrability is poor.

Claims (8)

1. The preparation method of the mesoporous-macroporous double-pore distribution alumina spherical particles is characterized by comprising the following steps: (1) Uniformly mixing water, low-carbon alcohol, inorganic aluminum salt, starch and sesbania powder, heating to 50-60 ℃, and then adding alkylene oxide to form a uniform mixture a; (2) Dripping the mixture a obtained in the step (1) into melted vaseline to form gel balls, performing first aging and washing on the gel balls in the vaseline, performing second aging in an alkaline aqueous solution, and performing washing, drying and roasting on the gel balls after the second aging to obtain a product; in the alumina spherical particles, the mesoporous size ranges from 10 nm to 30nm, the pore volume ratio is 30% -70%, the macroporous size distribution is 100-400nm, and the pore volume ratio is 20-60%;
the lower alcohol in the step (1) is methanol and/or ethanol;
based on the weight of the mixture a obtained in the step (1), the following substances are added: 20-35% of water, 15-35% of low-carbon alcohol, 15-35% of inorganic aluminum salt, 1-5% of starch, 1-5% of sesbania powder and 10-35% of alkylene oxide;
the first aging condition in the step (2) is as follows: aging at 60-90deg.C for 12-48 hr;
the second aging in the step (2) is carried out in a closed container, the aging time is 1-12 hours, the temperature is 100-200 ℃, and the pressure is the autogenous pressure of the closed container; the alkaline aqueous solution is ammonium bicarbonate or urea aqueous solution, the mass percentage concentration is 5% -30%, and the dosage of the alkaline aqueous solution at least meets the requirement of completely submerging the treated gel balls.
2. The method according to claim 1, characterized in that: spherical particles having a diameter of 0.5 to 1.5mm, a crushing strength of 50 to 100N/particle, an attrition rate of not more than 0.5wt%, and a BET specific surface area of 150 to 350m 2 Per g, pore volume of 0.5-1.0cm 3 /g。
3. The method according to claim 1, characterized in that: the inorganic aluminum salt in the step (1) is one or more of aluminum nitrate, aluminum chloride or aluminum sulfate.
4. The method according to claim 1, characterized in that: the starch in the step (1) is one or more of corn starch, wheat starch, sweet potato starch, lotus root starch or potato starch.
5. The method according to claim 1, characterized in that: the alkylene oxide in the step (1) is one or more of propylene oxide, butylene oxide or isomers with the same carbon number as the alkane.
6. The method according to claim 1, characterized in that: the melted Vaseline in the step (2) is in a liquid state, and the temperature is 60-90 ℃.
7. The method according to claim 1, characterized in that: and (3) after the first aging, washing with acetone, gasoline, benzene or toluene.
8. The method according to claim 1, characterized in that: the drying conditions in the step (2) are as follows: the drying temperature is 100-200 ℃ and the drying time is 12-24 hours; the roasting conditions are as follows: roasting temperature is 500-750 ℃ and roasting time is 1-12 hours.
CN202011493267.0A 2020-12-17 2020-12-17 Double-pore distribution alumina spherical particle and preparation method thereof Active CN114644352B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011493267.0A CN114644352B (en) 2020-12-17 2020-12-17 Double-pore distribution alumina spherical particle and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011493267.0A CN114644352B (en) 2020-12-17 2020-12-17 Double-pore distribution alumina spherical particle and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114644352A CN114644352A (en) 2022-06-21
CN114644352B true CN114644352B (en) 2024-02-13

Family

ID=81991415

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011493267.0A Active CN114644352B (en) 2020-12-17 2020-12-17 Double-pore distribution alumina spherical particle and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114644352B (en)

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB739396A (en) * 1952-08-15 1955-10-26 Universal Oil Prod Co Manufacture of spheroidal alumina
US3714071A (en) * 1970-03-18 1973-01-30 Universal Oil Prod Co Low density alumina spheres of improved strength at high temperature
WO2001045838A1 (en) * 1999-12-21 2001-06-28 W.R. Grace & Co.-Conn. Alumina trihydrate derived high pore volume, high surface area aluminum oxide composites and methods of their preparation and use
CN1488441A (en) * 2002-10-10 2004-04-14 中国石油化工股份有限公司 Method for preparing alumina supporter
CN101549287A (en) * 2009-05-15 2009-10-07 北京化工大学 A high intensity spherical zirconium-containing alumina and method of preparing the same
CN101935060A (en) * 2010-08-09 2011-01-05 吉林大学 Method for preparing modified alumina sol suitable for oil ammonia column forming
CN102838143A (en) * 2011-06-23 2012-12-26 中国石油化工股份有限公司 Preparation method for spherical alumina
CN103055950A (en) * 2011-10-21 2013-04-24 中国石油化工股份有限公司 Method for preparing spherical aluminum oxide
JP2014129235A (en) * 2014-03-25 2014-07-10 Tohoku Univ Tabular powder and cosmetic containing the same
CN105621464A (en) * 2014-10-30 2016-06-01 中国石油化工股份有限公司 Synthetic method of aluminium oxide
CN106111214A (en) * 2015-05-07 2016-11-16 Ifp 新能源公司 There is the spherical alumina granule of mechanical strength that count diameter in the macropore of 0.05 to 30 μm, that have improvement
CN107651702A (en) * 2017-10-09 2018-02-02 齐鲁工业大学 A kind of mesoporous γ Al2O3The preparation method of cotton-shaped microballoon
CN108658108A (en) * 2018-05-28 2018-10-16 武汉理工大学 A kind of preparation method of hollow aluminum oxide microspheres
CN110467206A (en) * 2018-05-11 2019-11-19 中国石油化工股份有限公司 A kind of macroporous aluminium oxide and preparation method thereof
CN111298802A (en) * 2018-12-12 2020-06-19 中国石油化工股份有限公司 Preparation method of flue gas denitration catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA011732B1 (en) * 2005-03-01 2009-04-28 Карбо Керамикс Инк. Methods for producing sintered particles from a slurry of an alumina-containing raw material

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB739396A (en) * 1952-08-15 1955-10-26 Universal Oil Prod Co Manufacture of spheroidal alumina
US3714071A (en) * 1970-03-18 1973-01-30 Universal Oil Prod Co Low density alumina spheres of improved strength at high temperature
WO2001045838A1 (en) * 1999-12-21 2001-06-28 W.R. Grace & Co.-Conn. Alumina trihydrate derived high pore volume, high surface area aluminum oxide composites and methods of their preparation and use
CN1488441A (en) * 2002-10-10 2004-04-14 中国石油化工股份有限公司 Method for preparing alumina supporter
CN101549287A (en) * 2009-05-15 2009-10-07 北京化工大学 A high intensity spherical zirconium-containing alumina and method of preparing the same
CN101935060A (en) * 2010-08-09 2011-01-05 吉林大学 Method for preparing modified alumina sol suitable for oil ammonia column forming
CN102838143A (en) * 2011-06-23 2012-12-26 中国石油化工股份有限公司 Preparation method for spherical alumina
CN103055950A (en) * 2011-10-21 2013-04-24 中国石油化工股份有限公司 Method for preparing spherical aluminum oxide
JP2014129235A (en) * 2014-03-25 2014-07-10 Tohoku Univ Tabular powder and cosmetic containing the same
CN105621464A (en) * 2014-10-30 2016-06-01 中国石油化工股份有限公司 Synthetic method of aluminium oxide
CN106111214A (en) * 2015-05-07 2016-11-16 Ifp 新能源公司 There is the spherical alumina granule of mechanical strength that count diameter in the macropore of 0.05 to 30 μm, that have improvement
CN107651702A (en) * 2017-10-09 2018-02-02 齐鲁工业大学 A kind of mesoporous γ Al2O3The preparation method of cotton-shaped microballoon
CN110467206A (en) * 2018-05-11 2019-11-19 中国石油化工股份有限公司 A kind of macroporous aluminium oxide and preparation method thereof
CN108658108A (en) * 2018-05-28 2018-10-16 武汉理工大学 A kind of preparation method of hollow aluminum oxide microspheres
CN111298802A (en) * 2018-12-12 2020-06-19 中国石油化工股份有限公司 Preparation method of flue gas denitration catalyst

Also Published As

Publication number Publication date
CN114644352A (en) 2022-06-21

Similar Documents

Publication Publication Date Title
US4081406A (en) Preparation of catalysts of predetermined pore size distribution and pore volume
US3669904A (en) Particles featuring gamma alumina
US7172990B2 (en) Highly active spherical metal support catalysts
CN108855024B (en) Preparation method of alumina carrier with large aperture and high mechanical strength
US5021378A (en) Molded articles based on pyrogenically prepared silicon dioxide, process for their production and their use
CN106747591B (en) A kind of macropore holds the preparation method of alumina support
RU2753336C1 (en) Carrier material from aluminium oxide and method for production thereof, hydrogenation catalyst and method for hydrogenation of residual oil
EP1473082A1 (en) Method for preparing hydrogenation purification catalyst
CN109420504B (en) Catalytic gasoline hydrodesulfurization catalyst and preparation method thereof
US3980552A (en) Hydrodesulfurization of residual petroleum oil with a sulfided cobalt-molybdenum-alumina catalyst
CN114644352B (en) Double-pore distribution alumina spherical particle and preparation method thereof
CN114644353B (en) Preparation method of three-dimensional through macroporous alumina
US4081405A (en) Preparation of catalysts of predetermined pore size distribution and pore volume
US4145316A (en) Preparation of catalysts of predetermined pore size distribution and pore volume
CN107913742B (en) Alumina carrier containing macropores and preparation method thereof
CN107983326B (en) Preparation method of hydrogenation catalyst forming carrier
CN114634194B (en) Spherical three-dimensional through macroporous alumina and preparation method thereof
US4980334A (en) Macroporous alumina/diatomaceous earth bio-supports
CN114644351B (en) Superfine alumina spherical particles and preparation method thereof
CN114516649B (en) Spherical alumina with super macroporous structure and preparation method thereof
CN103480338B (en) Article shaped containing hydrated alumina and preparation method thereof and aluminium oxide article shaped and application
CN112742408B (en) Dry gas hydrogenation saturated olefin and desulfurization catalyst, and preparation method and application thereof
CN112742391B (en) Natural gas hydrodesulfurization catalyst and preparation and application thereof
RU2698191C1 (en) Catalyst for protective layer for processing of heavy oil feedstock
GB1570632A (en) Preparation of catalysts of predetermined pore size distribution and pore volume

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20240105

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Applicant after: CHINA PETROLEUM & CHEMICAL Corp.

Applicant after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Applicant before: CHINA PETROLEUM & CHEMICAL Corp.

Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.

GR01 Patent grant
GR01 Patent grant