CN101940954B - Method for preparing alumina supporters - Google Patents
Method for preparing alumina supporters Download PDFInfo
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- CN101940954B CN101940954B CN200910012482A CN200910012482A CN101940954B CN 101940954 B CN101940954 B CN 101940954B CN 200910012482 A CN200910012482 A CN 200910012482A CN 200910012482 A CN200910012482 A CN 200910012482A CN 101940954 B CN101940954 B CN 101940954B
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Abstract
The invention discloses a method for preparing alumina supporters. The method comprises the following steps of: mixing micron-sized slender fungi serving as a template, aluminum hydroxide raw powder and an adhesive to obtain a mixture; and molding, drying and baking the mixture to obtain the alumina supporters. Pores of alumina can be enlarged by selecting the fungi with appropriate diameters according to actual macromolecular reactants and resultants, and the micron-sized pores have high penetrability, which contributes to the reaction and diffusion of macromolecular substances.
Description
Technical field
The present invention relates to a kind of preparation method of alumina support, relate in particular to a kind of preparation method of micron order through hole alumina support.
Background technology
Aluminium oxide is the most important carrier of catalyst, is widely used in petrochemical industry.At present, catalyst is to be carrier with the aluminium oxide basically.Synthetic method mainly contains aluminum sulfate method and carbonizatin method, and its duct is the mesopore that is barricaded as between the nano particle, and channel diameter is less, is not suitable for macromolecular substances and reacts and spread.
At present, adopt physics and/or chemical method reaming usually, increase the duct, large aperture.CN1068975A has proposed the preparation method of a kind of low-density, large pore volume, high-strength alumina carrier.This method is following: aluminium salt or aluminate obtain boehmite through neutralization, obtain aluminium colloidal sol with acid treatment, and adding granularity is that the following alumina powder of 200 orders is mixed well; And then the adding gelling agent, through forming oil column, aging, dry, roasting prepares γ-Al
2O
3This method mainly is through the method reaming of gelling agent pyrolysis.CN1087289A proposes γ-Al
2O
3The aqueous particulate material of precursor, moment is warming up to 500～650 ℃, and at high temperature keeps several hours, the preparation macropore alumina supporter.CN1597117A grinds to form powder with the aluminium oxide leftover bits and pieces, then with carbon powder and nitrogenous aqueous slkali or fully the volatile ammonium salt alkaline aqueous solution mix and pinch, add the aluminum hydroxide solid elastomer powder again, mix and pinch into plastic; After moulding, drying, roasting, make alumina support; The expanding method that this patent adopts physics and chemofacies to combine.Above-mentioned patent disclosed method is to adopt powdery or liquid expanding agent, though the ability reaming, the penetrability in duct, large aperture is relatively poor.
Summary of the invention
To the problem that prior art exists, the present invention proposes a kind of preparation method of alumina support.This method can prepare and has the good alumina support of micron order duct penetrability.
The preparation method of alumina support of the present invention comprises the steps:
(1) template, the former powder of aluminium hydroxide and adhesive are mixed;
(2) after moulding, through oven dry and roasting, obtain alumina support of the present invention again.
Described template is that micron-sized mushroom is biological; Be shaped as bar-shaped, wire and/or dendroid; Its diameter can decide according to the size of the raw material that will process and product molecule, and general diameter is 1～5 μ m, and length preferably is not less than 10 μ m; Be not higher than 1000 μ m, derive from yeast fungus strain, unwrapping wire fungus strain and the mould fungus strain one or more.The addition of said template is 5%～40% of the former grain weight amount of aluminium hydroxide.
Template of the present invention is preferably passed through preliminary treatment, and the preprocessing solution that is adopted is a potassium dihydrogen phosphate, and the preprocess method that is adopted is washing.But controlling the potassium oxide weight content that potassium dihydrogen phosphate brings in the alumina support is 0.2%～2.0%.
The former powder of described aluminium hydroxide can be the pure thin water-aluminum hydroxide of plan; It also can be the thin water-aluminum hydroxide of plan that contains various auxiliary agents; Wherein auxiliary agent can be one or more in silicon, titanium, zirconium, boron, magnesium, calcium, phosphorus, nitrogen and the carbon, and this auxiliary agent is generally hydroxide or oxide form.
Described adhesive derives from inorganic acid and/or organic acid, and described inorganic acid is one or more in hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, the perchloric acid etc., and described organic acid is one or more in formic acid, acetate, oxalic acid, glacial acetic acid and the citric acid.Described adhesive can also comprise one or more in water, ethanol, the methyl alcohol isopolarity solvent.
The mixture of step (1) gained can adopt conventional forming method moulding, generally adopts the extruded moulding method.Described oven dry and method of roasting also can adopt conventional method, and general described drying condition is: dried 5～24 hours for 80～110 ℃; Described roasting condition was: 300～650 ℃ of bubbling airs or inert gas (nitrogen) roasting 3～24 hours.
The micron order through hole alumina support of the inventive method gained can be used for that hydrofinishing, hydrocracking, isomerization, alkylation, catalytic cracking, alkene are saturated, alkene oligomerization, catalytic reforming, hydrogenation dearomatization, Aromatizatian catalytic agent carrier.
The aluminium oxide of the inventive method gained has the micron order through hole; Wherein aluminium oxide is the reaction position; And bacteriogenic micron order through hole is the diffusion position; Be especially suitable for use as residual oil hydrocatalyst carrier,, especially be used as the deposition of metals such as iron, calcium, magnesium, nickel, vanadium like Hydrodemetalation catalyst, hydrodesulfurization, hydrodenitrogenation catalyst carrier.
The advantage of the aluminium oxide that the inventive method is prepared is following:
1, bar-shaped mushroom has formed and has had the micron order through hole, and the reaction and the diffusion admittance of macromolecular reaction thing is provided, and the diffusion admittance of big molecule product.
2, this aluminium oxide can select the mushroom of suitable diameter come reaming according to the macromolecular reaction thing of reality and product, and this aluminium oxide by reaming after, the volume of its specific area and mesopore and aperture does not have tangible change.
3, the liquid potassium dihydrogen phosphate is adopted in the template preliminary treatment, helps the effect of demetalization reaction and reduction carbon deposit.
4, mushroom template wide material sources.
5, preparation technology is simple, and is easy to implement.
Description of drawings
Fig. 1 is ESEM (SEM) figure of Comparative Examples 2 gained alumina supports.
Fig. 2 is ESEM (SEM) figure of embodiment 1 gained alumina support.
Fig. 3 is ESEM (SEM) figure of embodiment 1 gained alumina support
The specific embodiment
Specific surface of the present invention and porous adopt the liquid nitrogen cryogenics absorption method, and exterior appearance adopts scanning electron microscope analysis.
Below in conjunction with embodiment the present invention is further specified.
Comparative Examples 1
Add after 3g nitric acid and 180ml water mixes with the 200g macropore aluminium hydrate powder of 200g carbonizatin method production, extruded moulding then under air atmosphere, in 100 ℃ of dryings 5 hours, 450 ℃ of following roastings 8 hours, obtains alumina support D1, and its character is seen table 1.
Comparative Examples 2
Add after 3g nitric acid, 180ml water and 8g carbon black mix with the macropore aluminium hydrate powder of 200g carbonizatin method production, extruded moulding is then under air atmosphere; In 100 ℃ of dryings 5 hours; 450 ℃ of following roastings 8 hours, obtain the D2 of alumina support, its character is seen table 1.
Embodiment 1
The used template of present embodiment is that bar-shaped diameter is 2 μ m, and length is the saccharomycete of 10～1000 μ m.Saccharomycete obtains through fermentation method, with the saturated solution of phosphoric acid potassium dihydrogen washing fermentate 3 times.
Add after 3g nitric acid, 180ml water and 60g saccharomycete mix with the macropore aluminium hydrate powder of 200g carbonizatin method production, extruded moulding is then under air atmosphere; In 100 ℃ of dryings 5 hours; 450 ℃ of following roastings 8 hours, obtain alumina support A1, its character is seen table 1.
Embodiment 2
The used template of present embodiment is that bar-shaped diameter is 2 μ m, and length is the saccharomycete of 10～1000 μ m.Saccharomycete obtains through fermentation method, with the saturated solution of phosphoric acid potassium dihydrogen washing fermentate 3 times.
Add after 3g nitric acid, 180ml water and 30g saccharomycete mix with the macropore aluminium hydrate powder of 200g carbonizatin method production, extruded moulding is then under air atmosphere; In 100 ℃ of dryings 5 hours; 450 ℃ of following roastings 8 hours, obtain alumina support A2, its character is seen table 1.。
The character of table 1 embodiment of the invention and Comparative Examples alumina support
| Sample | D1 | D2 | A1 | A2 |
| Pore volume/cm 3·g -1 | 0.6 | 0.65 | 0.71 | 0.69 |
| Specific surface/m 2·g -1 | 266 | 273 | 281 | 276 |
| Average pore diameter/nm | 9 | 9.5 | 10.1 | 9.9 |
| Pore size distribution, % | ||||
| ＜10nm | 91 | 80 | 63 | 76 |
| 10-100nm | 8 | 6 | 4 | 8 |
| ＞300nm | 1 | 14 | 33 | 16 |
| Porosity/% | 78 | 80 | 82 | 85 |
| Intensity, N/mm | 7 | 12 | 8 | 18 |
Claims (6)
1. the preparation method of an alumina support comprises the steps:
(1) template, the former powder of aluminium hydroxide and adhesive are mixed, the former powder of described aluminium hydroxide is for intending thin water-aluminum hydroxide;
(2) after moulding, through oven dry and roasting, obtain alumina support again;
Described template is micron-sized mushroom, is shaped as bar-shaped; The diameter of said micron-sized mushroom is 1～5 μ m, and length is not less than 10 μ m and is not higher than 1000 μ m, and the addition of said template is 5%～40% of the former grain weight amount of aluminium hydroxide.
2. according to the described method of claim 1, it is characterized in that said micron-sized mushroom derives from one or more in yeast fungus strain, unwrapping wire fungus strain and the mould fungus strain.
3. according to the described method of claim 1; It is characterized in that described template is through preliminary treatment; The preprocessing solution that is adopted is a potassium dihydrogen phosphate; The preprocess method that is adopted is washing, and the potassium oxide weight content that control is brought in the alumina support by potassium dihydrogen phosphate is 0.2%～2.0%.
4. according to the described method of claim 1; It is characterized in that the former powder of described aluminium hydroxide is the thin water-aluminum hydroxide of plan that contains auxiliary agent; Wherein auxiliary agent is one or more in silicon, titanium, zirconium, boron, magnesium, calcium, phosphorus, nitrogen and the carbon, and this auxiliary agent is hydroxide or oxide form.
5. according to the described method of claim 1; It is characterized in that described adhesive derives from inorganic acid and/or organic acid; Described inorganic acid is one or more in hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, the perchloric acid, and described organic acid is one or more in formic acid, acetate, oxalic acid and the citric acid.
6. according to the described method of claim 1, it is characterized in that the described drying condition of step (2) is: dried 5～24 hours for 80～110 ℃; Described roasting condition was: 300～650 ℃ of bubbling airs or inert gas roasting 3～24 hours.
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| CN101940954B true CN101940954B (en) | 2012-10-17 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10676401B2 (en) * | 2018-04-23 | 2020-06-09 | Scientific Design Company, Inc. | Porous bodies with enhanced pore architecture prepared with oxalic acid |
| CN112717947A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Boron-containing catalyst and preparation method and application thereof |
| CN112718013A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Alumina carrier and preparation and application thereof |
| CN114426527B (en) * | 2020-10-15 | 2023-11-10 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene oxide, preparation method and silver catalyst and application |
| CN114433053B (en) * | 2020-10-19 | 2023-10-10 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN114433174B (en) * | 2020-10-19 | 2024-05-07 | 中国石油化工股份有限公司 | Silicon-aluminum carrier and preparation method and application thereof |
| CN114433184B (en) * | 2020-10-19 | 2024-05-07 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005193110A (en) * | 2004-01-05 | 2005-07-21 | Chiyoda Corp | Synthetic gas producing catalyst and method for producing synthetic gas by using the same |
| US20080026041A1 (en) * | 2005-09-12 | 2008-01-31 | Argonide Corporation | Non-woven media incorporating ultrafine or nanosize powders |
| CN101254470A (en) * | 2007-02-28 | 2008-09-03 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene with ethylene and butene inverse-disproportionation and method of preparing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005193110A (en) * | 2004-01-05 | 2005-07-21 | Chiyoda Corp | Synthetic gas producing catalyst and method for producing synthetic gas by using the same |
| US20080026041A1 (en) * | 2005-09-12 | 2008-01-31 | Argonide Corporation | Non-woven media incorporating ultrafine or nanosize powders |
| CN101254470A (en) * | 2007-02-28 | 2008-09-03 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene with ethylene and butene inverse-disproportionation and method of preparing the same |
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| Title |
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| JP特开2005193110A 2005.07.21 |
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