CN114634370B - High-strength capsule hole alumina material and preparation method thereof - Google Patents
High-strength capsule hole alumina material and preparation method thereof Download PDFInfo
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- CN114634370B CN114634370B CN202011478642.4A CN202011478642A CN114634370B CN 114634370 B CN114634370 B CN 114634370B CN 202011478642 A CN202011478642 A CN 202011478642A CN 114634370 B CN114634370 B CN 114634370B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002775 capsule Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229920002472 Starch Polymers 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- 235000019698 starch Nutrition 0.000 claims abstract description 15
- 239000008107 starch Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 11
- 239000012798 spherical particle Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 229940099259 vaseline Drugs 0.000 claims abstract description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004537 pulping Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229920002261 Corn starch Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 240000002853 Nelumbo nucifera Species 0.000 claims description 4
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000008120 corn starch Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229920001592 potato starch Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 7
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 2
- 239000003223 protective agent Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
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Abstract
The invention discloses a high-strength capsule cell alumina material and a preparation method thereof. In the spherical alumina of the invention, the volume content of the capsule holes is 5-60%, the crushing strength is 10-50N/particle, and the BET specific surface area is 100-350m 2 And/g. The preparation method comprises the following steps: (1) Uniformly mixing an alumina precursor, calcium carbonate powder, water, a surfactant and starch, and pulping to be uniform; (2) Dripping the mixture obtained in the step (1) into melted vaseline to form liquid drop balls, aging, filtering, drying, roasting, and performing hydro-thermal treatment by adopting acid liquor; (3) And (3) washing, drying and roasting the material obtained in the step (2) to obtain the capsule hole alumina spherical particles. The high-strength capsule cell alumina material has high mechanical strength, can meet the strength requirement of the existing heterogeneous catalytic reaction, and can be used as a heterogeneous catalyst carrier, a filler or a protective agent.
Description
Technical Field
The invention belongs to the field of inorganic material preparation, and relates to a high-strength capsule cell alumina material and a preparation method thereof.
Background
Porous alumina is widely used as a support material for heterogeneous catalysts. The pore structure is an important physicochemical property of the catalyst, and in general, the characteristics of the pore have a decisive influence on the catalytic performance. For the catalytic reaction participated by the macromolecular material, the catalyst also needs to have a macroporous or even super macroporous (more than 1000 nm) structure so as to further improve the mass transfer capability of the macromolecular material.
Physicochemical journal, 2006, 22 (7): 831-835 provides a preparation method of macroporous alumina material, which comprises mixing polystyrene particles with alumina precursor, processing to obtain vesicle macroporous alumina, wherein the obtained material has low physical strength, can not be prepared into a fixed shape, and has high cost of the polystyrene particles and serious environmental pollution.
CN 201010221297.6 is prepared by mixing an aluminum source, polyethylene glycol, low-carbon alcohol, water and alkylene oxide, and has vesicle-shaped macropores with the pore diameter of 0.05-10 mu m, the alkylene oxide and other raw materials used by the method are expensive, the preparation cost is high, and the material obtained by the method does not have a fixed shape in appearance, so that the material is not beneficial to being filled in a reactor to control mass transfer of materials and pressure drop of a bed layer.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-strength capsule hole alumina material and a preparation method thereof. The high-strength capsule cell alumina material has high mechanical strength, can meet the strength requirement of the existing heterogeneous catalytic reaction, and can be used as a heterogeneous catalyst carrier, a filler or a protective agent.
The high-strength capsule cell alumina material has a spherical particle shape, the diameter of the spherical particle is 1-5mm, the average pore diameter of the capsule cells is more than 500nm and less than 5000nm, and the content of the capsule cells is 5-60% by volume; the spherical particles have a crush strength of 10 to 50N/particle and a BET specific surface area of 100 to 350m 2 /g。
The preparation method of the high-strength capsule cell alumina material comprises the following steps:
(1) Uniformly mixing an alumina precursor, calcium carbonate powder, water, a surfactant and starch, and pulping to form a uniform sol-like mixture;
(2) Dripping the sol-like mixture obtained in the step (1) into melted vaseline to form liquid drop balls, aging, separating gel balls, and performing drying, roasting and acid liquor hydro-thermal treatment on the gel balls;
(3) And (3) washing, drying and roasting the product obtained in the step (2) to obtain the high-strength capsule-cell alumina material.
In the method of the invention, the alumina precursor in the step (1) is pseudo-boehmite powder, or pseudo-boehmite powder modified by elements such as silicon, boron, phosphorus, titanium or zirconium, or aluminum oxide which can be converted into alumina after roasting, and aluminum oxide which can be converted into oxide after roasting and is modified by elements such as silicon, boron, phosphorus, titanium or zirconium.
In the method of the invention, the calcium carbonate powder in the step (1) has the particle size of 500-5000nm and the shape of sphere or nearly sphere.
In the method of the present invention, the surfactant in the step (1) is one or more of sulfonate anionic surfactants, including but not limited to one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and the like.
In the method of the invention, the starch in the step (1) is corn starch, lotus root starch, potato starch or a mixture of any proportion thereof.
In the method, the beating in the step (1) is performed by means of mechanical stirring (including shearing stirring), magnetic stirring and the like, the beating degree meets the requirement of slurry sol, and the slurry sol is kept stable at least at room temperature for 30 minutes without obvious layering and precipitation phenomena. The beating temperature of the mixed materials in the step is kept at 80-100 ℃ and the beating time is 5-30 minutes.
In the method of the invention, based on the weight of the mixture obtained in the step (1), the water is added in an amount of 30 to 70wt%, the alumina precursor is added in an amount of 10 to 50wt%, the calcium carbonate powder is added in an amount of 5 to 25wt%, the surfactant is added in an amount of 0.5 to 10wt%, and the starch is added in an amount of 1 to 15wt%.
In the method of the invention, the vaseline in the step (2) is in a liquid state and the temperature is 50-80 DEG C
In the method of the invention, the aging conditions in the step (2) are as follows: aging at 50-80deg.C for 0.5-6 hr.
In the process of the invention, the drying described in step (2) is carried out at a temperature of not more than 150℃and preferably 40-120℃for 12-48 hours.
In the method of the invention, the acid liquor in the step (2) is one or more of hydrochloric acid, nitric acid or acetic acid, preferably acetic acid; the concentration of the acid solution is 0.1-3mol/L, preferably 0.5-2mol/L. The acid liquor is used in an amount sufficient to completely submerge the solid material in the container.
In the method of the present invention, the firing conditions described in step (2): the temperature is 300-550 ℃, and the roasting time is 0.5-12 hours.
In the method of the invention, the acid liquid hydrothermal reflux treatment condition in the step (2) is as follows: the hydrothermal treatment temperature is 50-100 ℃, and the hydrothermal treatment time is 0.5-6 hours. Generally, the process is carried out in an atmospheric vessel.
In the method of the invention, the medium used in the washing in the step (3) is water, and the washing degree is up to the neutral or near neutral pH value of the washing liquid.
In the process of the invention, the drying in step (3) is carried out at a temperature of not more than 200℃and preferably at a temperature of 100 to 150℃for a period of 12 to 24 hours.
In the method of the present invention, the firing conditions described in step (3): the temperature is 450-750 ℃ and the roasting time is 1-12 hours.
The capsule cell alumina material has higher crushing strength, contains the capsule cells with controllable content and aperture, can be used as a carrier of heterogeneous catalysts, and is applied to specific reaction processes in various macromolecular catalytic reactions, such as residual oil and wax oil hydrogenation reactions.
Drawings
Fig. 1 is an optical camera photograph of the high-strength capsule hole alumina spherical particles prepared in example 1.
FIG. 2 is a scanning electron microscope image of the high-strength capsule hole alumina spherical particles prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples. In the present invention, the diameters of 100 particles were randomly measured with a vernier caliper, and the average diameter was calculated. And observing the shape of the capsule holes by using a scanning electron microscope, and measuring the sizes of the pore channels. Specific surface area was measured by BET method, and mechanical strength of the support was measured by DL 3-type intensity meter. Calculation of the volume content of vesicle macropores: and observing the section of the sample by adopting a scanning electron microscope, searching for the largest capsule hole and the smallest capsule hole, calculating the average diameter value of the capsule holes, taking the average diameter value as the thickness of the section to obtain the volume of the section, calculating the total volume of all the capsule holes observed by the section, and multiplying the total volume by 100% of the volume of the capsule holes compared with the volume of the section to obtain the volume content of the capsule holes.
Example 1
Water, SB powder, calcium carbonate powder (average particle size: 1100 nm), sodium dodecylbenzenesulfonate and corn starch were mixed uniformly at room temperature, and the mixture was made into a stable sol by using a shearing stirrer, and the final system temperature was brought to 95 ℃. The mixture comprises the following components in parts by weight: 60% of water, 30% of SB powder, 3% of calcium carbonate powder, 1% of sodium dodecyl benzene sulfonate and 6% of starch. Dropping the sol into liquid vaseline at 70 deg.c to form liquid drop, ageing for 5 hr, filtering to obtain gel ball, stoving at 90 deg.c for 12 hr, roasting at 500 deg.c for 5 hr, soaking in 2.0mol/L acetic acid solution, hydrothermal reflux treatment at 60 deg.c for 3 hr, filtering with distilled water to wash until the washing liquid is near neutral, drying at 120 deg.c and roasting at 550 deg.c for 3 hr to obtain final sample.
The obtained product was spherical particles of uniform size with an average diameter of 1.7mm. The product is observed by a scanning electron microscope to form a particle section, and the particle section has capsule holes with the diameter of about 0.8 mu m, the volume content of the large holes of the capsule is 11 percent, the crushing strength of the material is 12N/particle, and the BET specific surface area is 256m 2 /g。
Example 2
Water, SB powder, calcium carbonate powder (average particle diameter 2500 nm), sodium dodecyl sulfate, potato starch were mixed uniformly at room temperature, and the mixture was made into a stable sol by using a shear mixer, and the final system temperature was brought to 80 ℃. The mixture comprises the following components in parts by weight: 50% of water, 30% of SB powder, 10% of calcium carbonate powder, 4% of sodium dodecyl sulfate and 6% of starch. Dropping the sol into liquid vaseline at 60 deg.c to form liquid drop, ageing for 5 hr, filtering to obtain gel ball, stoving at 120 deg.c for 12 hr, roasting at 500 deg.c for 5 hr, soaking in acetic acid solution of 0.5mol/L, hydrothermal reflux treatment at 70 deg.c for 3 hr, filtering with distilled water to wash until the washing liquid is near neutral, drying at 120 deg.c and roasting at 650 deg.c for 5 hr to obtain final sample.
The obtained product is spherical particles with uniform size and average diameter of 2mm. The product is observed by a scanning electron microscope to form a particle section, and the particle section has capsule holes with the diameter of about 2.3 mu m, the volume content of the large holes of the capsule is 18 percent, the crushing strength of the material is 13N/particle, and the BET specific surface area is 277m 2 /g。
Example 3
Water, alumina powder, calcium carbonate powder (average particle size 5000 nm), sodium dodecyl sulfate and lotus root starch are mixed uniformly at room temperature, and then a shearing stirrer is used to make the mixture into stable sol-like substance, so that the final system temperature reaches 100 ℃. The mixture comprises the following components in parts by weight: 40% of water, 25% of SB powder, 20% of calcium carbonate powder, 5% of sodium dodecyl sulfate and 10% of starch. Dropping the sol into liquid vaseline at 80 deg.c to form liquid drop, ageing for 5 hr, filtering to obtain gel ball, stoving at 120 deg.c for 12 hr, roasting at 500 deg.c for 5 hr, soaking in acetic acid solution of 0.5mol/L, hydrothermal reflux treatment at 80 deg.c for 3 hr, filtering with distilled water to wash until the washing liquid is near neutral, drying at 120 deg.c and roasting at 750 deg.c for 5 hr to obtain final sample.
The obtained product was spherical particles of uniform size with an average diameter of 2.5mm. The product is observed by a scanning electron microscope to form a particle section, the particle section has capsule holes with the diameter of about 4.7 mu m, the volume content of the large holes of the capsule is 39%, the crushing strength of the material is 17N/particle, and the BET specific surface area is 212m 2 /g。
Example 4
The calcium carbonate powder was replaced with an equal amount of water, and the other conditions were the same as in example 3. The obtained sample has compact section and no obvious capsule holes.
Comparative example 1
Materials were prepared as in example 1 of CN 201010221297.6, the resulting samples contained vesicle-like macropores, and the morphology of the resulting product was that of particles that did not have a fixed shape and determined size.
Claims (13)
1. A high strength capsule cell alumina material characterized by: the material has a spherical particle shape, the diameter is 1-5mm, the average pore diameter of the capsule holes is more than 500nm and less than 5000nm, and the content of the capsule holes is 5-60% by volume; crush strength of 10-50N/granule;
the high-strength capsule cell alumina material is prepared by the following method:
(1) Uniformly mixing an alumina precursor, calcium carbonate powder, water, a surfactant and starch, and pulping to form a uniform sol-like mixture;
(2) Dripping the sol-like mixture obtained in the step (1) into melted vaseline to form liquid drop balls, aging, separating gel balls, and performing drying, roasting and acid liquid hydrothermal reflux treatment on the gel balls;
(3) Washing, drying and roasting the product obtained in the step (2) to obtain a high-strength capsule cell alumina material;
in the step (2), the acid liquor is one or more of hydrochloric acid, nitric acid or acetic acid, and the concentration of the acid liquor is 0.1-3mol/L; acid liquor reflux water heat treatment conditions: the hydrothermal treatment temperature is 50-100 ℃, and the hydrothermal treatment time is 0.5-6 hours;
the roasting temperature in the step (2) is 300-550 ℃ and the roasting time is 0.5-12 hours.
2. The method for producing a high-strength capsule-cell alumina material according to claim 1, characterized by comprising the following: (1) Uniformly mixing an alumina precursor, calcium carbonate powder, water, a surfactant and starch, and pulping to form a uniform sol-like mixture; (2) Dripping the sol-like mixture obtained in the step (1) into melted vaseline to form liquid drop balls, aging, separating gel balls, and performing drying, roasting and acid liquid hydrothermal reflux treatment on the gel balls; (3) And (3) washing, drying and roasting the product obtained in the step (2) to obtain the high-strength capsule-cell alumina material.
3. The method according to claim 2, characterized in that: the alumina precursor in the step (1) is pseudo-boehmite powder, or pseudo-boehmite powder modified by silicon, boron, phosphorus, titanium or zirconium elements, or one or more of aluminum oxide compounds converted into alumina after roasting, and aluminum oxide compounds modified by silicon, boron, phosphorus, titanium or zirconium elements and converted into oxide after roasting.
4. The method according to claim 2, characterized in that: the calcium carbonate powder in the step (1) has the particle size of 500-5000nm.
5. The method according to claim 2, characterized in that: the surfactant in the step (1) is one or more of sulfonate anionic surfactants.
6. The method according to claim 5, wherein: the surfactant in the step (1) is one or more of sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate.
7. The method according to claim 2, characterized in that: the starch in the step (1) is corn starch, lotus root starch, potato starch or a mixture of the corn starch, the lotus root starch and the potato starch in any proportion.
8. The method according to claim 2, characterized in that: the sol-like mixture in the step (1) is kept stable at least at room temperature for 30 minutes, and no obvious layering or precipitation phenomenon exists; the pulping temperature is 80-100 ℃ and the pulping time is 5-30 minutes.
9. The method according to claim 2, characterized in that: based on the weight of the mixture obtained in the step (1), the adding amount of water is 30-70 wt%, the adding amount of alumina precursor is 10-50 wt%, the adding amount of calcium carbonate powder is 5-25 wt%, the adding amount of surfactant is 0.5-10 wt%, and the adding amount of starch is 1-15 wt%.
10. The method according to claim 2, characterized in that: the temperature of the melted Vaseline in the step (2) is 50-80 ℃.
11. The method according to claim 2, characterized in that: the aging conditions in the step (2) are as follows: aging at 50-80deg.C for 0.5-6 hr.
12. The method according to claim 2, characterized in that: the acid liquor in the step (2) is acetic acid; the acid liquor is used in an amount sufficient to completely submerge the solid material in the container.
13. Use of the capsule cell alumina material of claim 1 in a macromolecular catalytic reaction.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6617511A (en) * | 1965-12-13 | 1967-06-14 | ||
| CN1068975A (en) * | 1992-08-17 | 1993-02-17 | 中国石油化工总公司 | The preparation method of low-density, large pore volume, high-strength alumina carrier |
| CN101314467A (en) * | 2008-06-20 | 2008-12-03 | 大连理工大学 | One-step synthesis method for hollow carbon case |
| CN102659151A (en) * | 2012-04-24 | 2012-09-12 | 中国铝业股份有限公司 | Method for preparing spherical porous alumina carrier |
| CN102774842A (en) * | 2012-08-09 | 2012-11-14 | 中国石油大学(北京) | Porous organic-inorganic composite material and method for preparing same |
| CN103736524A (en) * | 2013-09-30 | 2014-04-23 | 四川蜀泰化工科技有限公司 | Preparation method of hydrocarbon conversion catalyst carrier |
| CN104353502A (en) * | 2014-11-12 | 2015-02-18 | 中国海洋石油总公司 | Preparation method of large-pore volume spherical aluminum oxide |
| FR3049595A1 (en) * | 2016-04-05 | 2017-10-06 | Ifp Energies Now | PROCESS FOR PREPARING A MESOPOROUS AND MACROPOROUS ALUMINA FROM AT LEAST ONE DAWSONITE PRECURSOR |
| CN108607617A (en) * | 2016-12-09 | 2018-10-02 | 中国石油化工股份有限公司 | A kind of method and silver catalyst preparing the alumina support for silver catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0611817A2 (en) * | 2005-06-07 | 2011-12-20 | Saint Gobain Ceramics | catalyst vehicle and a process for preparing the catalytic vehicle |
| FR3035798B1 (en) * | 2015-05-07 | 2017-04-28 | Ifp Energies Now | SPHEROIDAL ALUMINA PARTICLES OF IMPROVED MECHANICAL STRENGTH HAVING MEDIAN MACROPOROUS DIAMETER BETWEEN 0.05 AND 30 ΜM. |
-
2020
- 2020-12-16 CN CN202011478642.4A patent/CN114634370B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6617511A (en) * | 1965-12-13 | 1967-06-14 | ||
| CN1068975A (en) * | 1992-08-17 | 1993-02-17 | 中国石油化工总公司 | The preparation method of low-density, large pore volume, high-strength alumina carrier |
| CN101314467A (en) * | 2008-06-20 | 2008-12-03 | 大连理工大学 | One-step synthesis method for hollow carbon case |
| CN102659151A (en) * | 2012-04-24 | 2012-09-12 | 中国铝业股份有限公司 | Method for preparing spherical porous alumina carrier |
| CN102774842A (en) * | 2012-08-09 | 2012-11-14 | 中国石油大学(北京) | Porous organic-inorganic composite material and method for preparing same |
| CN103736524A (en) * | 2013-09-30 | 2014-04-23 | 四川蜀泰化工科技有限公司 | Preparation method of hydrocarbon conversion catalyst carrier |
| CN104353502A (en) * | 2014-11-12 | 2015-02-18 | 中国海洋石油总公司 | Preparation method of large-pore volume spherical aluminum oxide |
| FR3049595A1 (en) * | 2016-04-05 | 2017-10-06 | Ifp Energies Now | PROCESS FOR PREPARING A MESOPOROUS AND MACROPOROUS ALUMINA FROM AT LEAST ONE DAWSONITE PRECURSOR |
| CN108607617A (en) * | 2016-12-09 | 2018-10-02 | 中国石油化工股份有限公司 | A kind of method and silver catalyst preparing the alumina support for silver catalyst |
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