CN103769229B - A kind of method preparing the dry glue of silicon-containing alumina - Google Patents
A kind of method preparing the dry glue of silicon-containing alumina Download PDFInfo
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Abstract
The invention discloses a kind of method preparing the dry glue of silicon-containing alumina.The method comprises: mixed with weak acid and dispersant by clay original soil, then carries out hydrothermal treatment consists, then through pulverizing and sieving, obtaining granularity and being greater than 160 object modified clays; After clay alteration process, pulverize and sieve, added respectively by modified clay in the alkaline solution containing aluminium and the acid solution containing aluminium, then adopt under appropriate conditions and flow plastic, after filtration, washing, obtains the dry glue of silicon-containing alumina after drying.The method can make the aluminium oxide particles of clay and generation organically combine, and regulates the pore structure of silicon-containing alumina and the acidity of silicon-containing alumina, also can obtain uniform particle, pore distribution concentration silicon-containing alumina further.The dry glue of silicon-containing alumina of the present invention is applicable to the carrier component of heavy oil or residuum hydrogenating and metal-eliminating, hydrodesulfurization or hydrogenation conversion catalyst.
Description
Technical field
The present invention relates to the preparation method of the dry glue of a kind of silicon-containing alumina, particularly a kind of preparation method being applicable to the dry glue of silicon-containing alumina of heavy oil or catalyst for hydrotreatment of residual oil carrier material.
Background technology
In the preparation process of petroleum refining used catalyst, usually adopt aluminium oxide or silicon-containing alumina as carrier.Independent SiO
2only have more weak acidity, the acidity of aluminium oxide is also strong, and both be combined with each other and show very strong acidity.Much research shows, adds acidity, specific area that appropriate silica can improve aluminium oxide in aluminium oxide, is conducive to polymerization and hydrogenation reaction.And silicon-containing alumina has unique advantage, be successfully applied to the exploitation of multiple hydrogenation catalyst.The preparation method of silicon-containing alumina mainly contains the precipitation method, mixing method and infusion process.The nature difference of the silicon-containing alumina that different preparation methods obtains is larger.
USP4721696 describes a kind of preparation method of silicon-containing alumina, with aluminum nitrate and sodium aluminate for raw material, pH value is adopted to swing between 2 ~ 10, sodium metasilicate is added in the false colloidal sol of the aluminium hydroxide obtained, silicon-containing alumina is obtained after washing, drying, roasting, its silicone content is 1 ~ 30%, optimum 3-15%.The method preparation process is too complicated, and select sodium metasilicate to be silicon source, ensure to have comparatively low sodium content in product, washing process can produce a large amount of waste water, to environment simultaneously.
USP7186757 proposes a kind of method preparing silicon-containing alumina, is that wherein silicon source is sodium metasilicate by adopting the co-precipitation of Si-Al two kinds of gel mechanical mixture to prepare bimodal silicon-containing alumina.Owing to being that silicon-containing alumina is prepared in co-precipitation after simple and mechanical mixing, its sial combines more weak, and owing to selecting sodium metasilicate to be silicon source, ensure to have comparatively low sodium content in product, washing process can produce a large amount of waste water, to environment.
CN02109423.3 discloses a kind of preparation method of siliceous aluminium hydroxide, adopt carbonizatin method plastic, a certain amount of sodium metasilicate is added successively in plastic and ageing process, the silicon-containing alumina average pore size of preparation is 6-13nm, be applicable to heavy oil or residuum hydrodesulfurization or hydrodenitrogenation catalyst, for residuum hydrogenating and metal-eliminating reaction, its aperture is less, requires further improvement.
CN01118437.X describes a kind of preparation method of cracking catalyst for petroleum hydrocarbon, and it is by after clay slurry acid treatment, adds boehmite, water glass solution, adds Alumina gel, then add molecular sieve pulp, spraying dry, washing.The method is applicable to the preparation of the molecular sieve catalyst of silicon-aluminum containing matrix.The small-bore proportion of the catalyst <5nm of preparation is comparatively large, is not suitable for being used as heavy oil or residual oil hydrocatalyst material.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of the dry glue of a kind of silicon-containing alumina.The method can make the aluminium oxide particles of clay and generation organically combine, and regulates the pore structure of silicon-containing alumina and the acidity of silicon-containing alumina, also can obtain uniform particle, pore distribution concentration silicon-containing alumina further.The dry glue of silicon-containing alumina of the present invention is applicable to the carrier component of heavy oil or residuum hydrogenating and metal-eliminating, hydrodesulfurization or hydrogenation conversion catalyst.
The preparation method of the dry glue of silicon-containing alumina of the present invention, comprising:
(1) mixed with weak acid and dispersant by clay original soil, then carry out hydrothermal treatment consists, obtained modified clay, through pulverizing and sieving, obtains granularity and is greater than 160 object modified clays;
(2) modified clay that step (1) obtains is joined respectively in the alkaline solution containing aluminium and the acid solution containing aluminium, obtain alkaline slurry and acid slurries, wherein containing the temperature at least 50 DEG C of the acid solution of aluminium, be generally 50 DEG C ~ 95 DEG C, preferably 60 DEG C ~ 95 DEG C, more preferably 65 DEG C ~ 90 DEG C, containing the temperature at least 50 DEG C of the alkaline solution of aluminium, be generally 50 DEG C ~ 95 DEG C, preferably 60 DEG C ~ 95 DEG C, more preferably 65 DEG C ~ 90 DEG C
(3) add end water in plastic cans, then also stream adds the alkaline slurry of step (2) gained and acid slurries, controls gelling temperature at least 50 DEG C, be generally 50 DEG C ~ 95 DEG C, preferably 60 DEG C ~ 95 DEG C, more preferably 65 DEG C ~ 90 DEG C, controlling plastic pH value is 7.0 ~ 10.5, preferably 7.0 ~ 9.5;
(4) filtered by the slurries of step (4) gained, filter cake obtains the dry glue of silicon-containing alumina after washing, drying.
In the inventive method, preferably through Aging Step after step (3) plastic.Described aging referring to is being stirred or is being made solution keep the regular hour under inactive state.Aging temperature at least 50 DEG C, is generally 50 DEG C ~ 95 DEG C, preferably 60 DEG C ~ 95 DEG C, more preferably 65 DEG C ~ 90 DEG C.Ageing time is less than 90 minutes, is generally 10 ~ 90 minutes, preferably less than 60 minutes, more preferably 10 ~ 40 minutes.
In the inventive method, preferably in step (3) can according to product property need add organic expanding agent.Described organic expanding agent is one or more in the condensation product of alkyl phenol and oxirane, polyoxyethylene sorbitol acid anhydride list olein, AEO, polyoxyethylene stearic acid ester, its consumption is 0.1% ~ 10.0% of the dry glue weight of silicon-containing alumina, is preferably 0.3% ~ 8.0%.
In the inventive method, step (1) weak acid used is one or more of boric acid, acetic acid, citric acid, oxalic acid, tartaric acid etc., preferred boric acid or acetic acid.The concentration of weak acid used is 0.5 ~ 3mol/L.Described dispersant is one or more of polyethylene glycol, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polypropylene amine etc., wherein preferably polyethylene glycol or polyvinyl alcohol.The consumption of described dispersant is 5% ~ 20% of clay original soil weight.Generally every gram of clay original soil adds weak acid and disperses dosage to be less than 1mL, and the addition of preferred weak acid and dispersant is 0.3 ~ 0.9mL/g clay original soil.Described hydrothermal conditions is as follows: temperature is 400 DEG C ~ 700 DEG C, and the processing time is 1 ~ 8h, and processing pressure is 0.15 ~ 0.35MPa.Described clay is one or more of kaolin, imvite, galapectite, diatomite etc.
In the inventive method, in step (2), the alkaline solution added containing aluminium is 4:6 ~ 6:4 with the mass ratio of modified clay in the acid solution containing aluminium, is preferably 5:5.The described acid solution containing aluminium is the strong acid salt solution containing aluminium, one or more of preferably sulfuric acid aluminium, aluminum nitrate, aluminium chloride etc., more preferably sulfuric acid aluminium.Concentration containing the acid solution of aluminium is 20 ~ 50gAl
2o
3/ L, the described alkaline solution containing aluminium is alkali-metal meta-aluminate solution, and preferred sodium metaaluminate, potassium metaaluminate or their mixture, more preferred sodium metaaluminate, the concentration containing the alkaline solution of aluminium is 40 ~ 100gAl
2o
3/ L.
In the inventive method, containing aluminium acid solution with preferably differ within 5 DEG C containing the alkaline solution of aluminium and the gelling temperature of step (3), preferably identical.
In the inventive method, in plastic process, in plastic slurries, solid-to-liquid ratio is preferably constant, and solid-to-liquid ratio is 40 ~ 70g/L.Suitably dilution can be added as required, such as water in plastic cans.
In the inventive method, step (4) described drying condition: 100 DEG C ~ 150 DEG C dryings 2 ~ 6 hours, preferably 110 DEG C ~ 130 DEG C, dry 4 ~ 6 hours.
Described clay is one or more of kaolin, imvite, diatomite, attapulgite etc.
The dry glue of silicon-containing alumina prepared by the inventive method was through 500 DEG C ~ 950 DEG C roastings 2 ~ 6 hours, the character of gained silicon-containing alumina is as follows: the content of silica is 1wt% ~ 80wt%, preferred 1wt% ~ 60wt%, pore volume is 0.35 ~ 1.10mL/g, and specific area is 80 ~ 350m
2/ g, pore size distribution is as follows: the pore volume in the hole of bore dia < 6nm accounts for less than 20% of total pore volume, and the pore volume in the hole of bore dia > 15nm accounts for more than 30% of total pore volume.
Mesoporous property of the present invention and specific surface adopt the analysis of low temperature liquid nitrogen absorption method, and silica content adopts metric measurement, and siliceous structure of similar to thin diaspore adopts XRD to characterize.Meleic acid amount be adopt infrared spectrometer record, use adsorbent for pyridine.
The invention has the advantages that: in the dry glue of prepared silicon-containing alumina, the content of silica regulates simple, even and if silicone content is high more also can not produce a large amount of waste water.The present invention obtains modified clay by the method for hydrothermal treatment consists after adopting raw clay and weak acid and dispersant, the pore volume of this modified clay, surface area and acidity all have greatly improved, using this modified clay as silicon source, add in the acid solution containing aluminium and the alkaline solution containing aluminium respectively, modified clay reacts, to the further modification of clay with the acid solution containing aluminium and the alkaline solution containing aluminium further respectively at a certain temperature.Then adopt and flow plastic method plastic, thus Silicified breccias in clay is recombined after dissolving, introducing clay in this way can make the aluminium oxide particles of clay and generation organically combine, and regulates the pore structure of silicon-containing alumina and the acidity of silicon-containing alumina.Plastic reaction best equitemperature, etc. pH value and etc. carry out under solids content condition, the solid product particle making reaction generate like this is more even, pore size distribution is more concentrated.The dry glue of silicon-containing alumina of the present invention is applicable to the carrier component of heavy oil or residuum hydrogenating and metal-eliminating, hydrodesulfurization or hydrogenation conversion catalyst.
Accompanying drawing explanation
Fig. 1 is the XRD figure of embodiment 1 and comparative example 1, comparative example 2 gained silicon-containing alumina.
Detailed description of the invention
State technical characteristic of the present invention further below by embodiment, but be not limited to embodiment.Wt% is mass fraction.
Embodiment 1
Water-soluble to kaolin original soil 100g and 2.0mol/L acetic acid 50mL and 50mL 10g polyglycol solution of separating fully is mixed, and hydrothermal treatment device carries out modification, and hydrothermal treatment consists temperature is 600 DEG C, process 4h, hydrothermal treatment consists pressure 0.25MPa.Collected stand-by after pulverizing 160 mesh sieve after kaolin cooling after process.
Preparation sodium aluminate solution concentration is 80gAl
2o
3/ L amounts to 0.7L, be heated to 80 DEG C stand-by, aluminum sulfate solution concentration is 20gAl
2o
3/ L amounts to 2L, be heated to 80 DEG C stand-by.
In plastic cans, add 1.5L distilled water, be heated to 80 DEG C.Respectively take respectively 5g sieve after modified kaolin be put in sodium aluminate solution and aluminum sulfate solution, and stream adds above-mentioned two kinds of slurries, pH value is kept to be 8.5, be that 50g/L is constant by solid-to-liquid ratio in plastic cans, to calculate and stream adds time of water, and stream adds 1.0L distilled water, in plastic process, temperature remains on 80 DEG C.The ageing step is entered, ageing time 50min, aging temperature 80 DEG C after cemented into bundles.Slurries after the aging deionized water of 70 DEG C is washed till neutrality, and 110 DEG C of dryings 5 hours, obtain the dry glue of silicon-containing alumina, and 650 DEG C of roastings 3 hours, obtain silicon-containing alumina A, wherein SiO
2content be 5wt%.
Embodiment 2
Other condition, with embodiment 1, is just increased to 12g the amount of modified kaolin, prepares silicon-containing alumina B, wherein SiO
2content be 15wt%.
Embodiment 3
Other condition, with embodiment 1, is just changed to imvite kaolin, prepares silicon-containing alumina C, wherein SiO
2content be 5wt%.
Embodiment 4
Diatomite original soil 350g is fully mixed with the water-soluble 40g polyethylene glycol of 2.0mol/L acetic acid 150mL and 100g, hydrothermal treatment device carries out modification, hydrothermal treatment consists temperature is 700 DEG C, hydrothermal treatment consists pressure 0.30MPa, processing time 4h.Collected stand-by after pulverizing 160 mesh sieve after diatomite cooling after process.
Preparation sodium aluminate solution concentration is 50gAl
2o
3/ L amounts to 1.8L, be heated to 70 DEG C stand-by, aluminum sulfate solution concentration is 30gAl
2o
3/ L amounts to 1.0L, be heated to 70 DEG C stand-by.
In plastic cans, add 2.0L distilled water, be heated to 70 DEG C.Respectively take respectively 150g sieve after modification infusorial earth be put in sodium aluminate solution and aluminum sulfate solution, and stream adds above-mentioned two kinds of slurries, pH value is kept to be 7.0, be that 40g/L is constant by solid-to-liquid ratio in plastic cans, to calculate and stream adds time of water, and stream adds 2.2L distilled water, in plastic process, temperature remains on 70 DEG C.Add condensation product (OP-20) the 134mL(content 250g/L of organic expanding agent alkyl phenol and oxirane after cemented into bundles, calculate by the 8wt% of solids content).Enter the ageing step, ageing time 50min, aging temperature 70 DEG C.Slurries after the aging deionized water of 70 DEG C is washed till neutrality, and 100 DEG C of dryings 5 hours, obtain the dry glue of silicon-containing alumina, and 750 DEG C of roastings 2 hours, obtain silicon-containing alumina D, wherein SiO
2content be 50wt%.
Embodiment 5
Kaolin original soil 200g, original montmorillonoid soil 200g are fully mixed with the water-soluble 40g polyethylene glycol of 3.0mol/L acetic acid 250mL and 100mL, hydrothermal treatment device carries out modification, hydrothermal treatment consists temperature is 500 DEG C, hydrothermal treatment consists pressure 0.30MPa, processing time 4h.Collected stand-by after pulverizing 160 mesh sieve after mixed material cooling after process.
Preparation sodium aluminate solution concentration is 55gAl
2o
3/ L amounts to 1.8L, be heated to 80 DEG C stand-by, aluminum sulfate solution concentration is 20gAl
2o
3/ L amounts to 1.3L, be heated to 80 DEG C stand-by.
In plastic cans, add 0.7L distilled water, be heated to 80 DEG C.Respectively take respectively 180g sieve after modification material be put in aluminum sulfate solution and sodium aluminate solution, and stream adds above-mentioned two kinds of slurries, pH value is kept to be 8.0, be that 50g/L is constant by solid-to-liquid ratio in plastic cans, to calculate and stream adds time of water, and stream adds 1.8L distilled water, in plastic process, temperature remains on 80 DEG C.Add condensation product (OP-20) the 152mL(content 250g/L of organic expanding agent alkyl phenol and oxirane after cemented into bundles, calculate by the 8wt% of solids content).Enter the ageing step, ageing time 30min, aging temperature 80 DEG C.Slurries after the aging deionized water of 70 DEG C is washed till neutrality, and 110 DEG C of dryings 4 hours, obtain the dry glue of silicon-containing alumina, and 750 DEG C of roastings 3 hours, obtain silicon-containing alumina E, wherein SiO
2content be 50wt%.
Comparative example 1
Preparation sodium aluminate solution concentration is 80gAl
2o
3/ L amounts to 0.7L, be heated to 80 DEG C stand-by, aluminum sulfate solution concentration is 20gAl
2o
3/ L amounts to 2L, be heated to 80 DEG C stand-by.
In plastic cans, add 2.5L distilled water be heated to 80 DEG C.By the sodium aluminate solution prepared and aluminum sulfate solution and stream joins in plastic cans, keep gelling temperature 80 DEG C, plastic pH value 8.5.Waterglass 18.5g(SiO is added after cemented into bundles
2content 26wt%, calculates by solids content 5wt%), then enter the ageing step, ageing time 50min, aging temperature 80 DEG C.Slurries after the aging deionized water of 70 DEG C is washed till neutrality, and 110 DEG C of dryings 5 hours, obtain the dry glue of silicon-containing alumina, and 650 DEG C of roastings 3 hours, obtain silicon-containing alumina F.
Comparative example 2
Preparation sodium aluminate solution concentration is 80gAl
2o
3/ L amounts to 0.7L, be heated to 80 DEG C stand-by, aluminum sulfate solution concentration is 20gAl
2o
3/ L amounts to 2L, be heated to 80 DEG C stand-by.
In plastic cans, add the modified kaolin 10g after sieving in 2.5L distilled water and embodiment 1, be heated to 80 DEG C.And stream adds sodium aluminate solution and aluminum sulfate solution, keep pH value to be 8.5, in plastic process, temperature remains on 80 DEG C.The ageing step is entered, ageing time 50min, aging temperature 80 DEG C after cemented into bundles.Slurries after the aging deionized water of 70 DEG C is washed till neutrality, and 110 DEG C of dryings 5 hours, obtain the dry glue of silicon-containing alumina, and 650 DEG C of roastings 3 hours, obtain silicon-containing alumina G, wherein SiO
2content be 5wt%.
The physico-chemical property of silicon-containing alumina obtained above is listed in table 1, and XRD the results are shown in Figure 1.
table 1 silicon-containing alumina physico-chemical property
| Numbering | A | B | C | D | E | Comparative Example F | Comparative example G |
| Specific area, m 2/g | 326 | 294 | 312 | 193 | 142 | 388 | 354 |
| Pore volume, mL/g | 1.021 | 0.951 | 0.988 | 0.657 | 0.467 | 0.979 | 0.991 |
| Pore-size distribution, % | |||||||
| <6nm | 9.24 | 12.84 | 8.74 | 9.82 | 9.14 | 45.26 | 10.74 |
| 6-15nm | 57.01 | 47.95 | 53.02 | 44.25 | 40.68 | 38.13 | 52.48 |
| >15nm | 33.75 | 39.21 | 38.24 | 45.93 | 50.18 | 16.43 | 36.78 |
| SiO 2，wt% | 4.65 | 14.21 | 4.78 | 48.34 | 52.38 | 4.91 | 4.86 |
| Meleic acid amount, mmol/g | 0.332 | 0.365 | 0.341 | 0.399 | 0.407 | 0.215 | 0.312 |
As can be seen from Table 1: when in aluminium oxide containing close silica time, in plastic raw material, add clay material be silicon source and add compared with sodium metasilicate, and aperture ratio significantly reduces and pore distribution concentration, too increases the acidity of aluminium oxide simultaneously.As can be seen from Figure 1: employing clay material is that the XRD of silicon-containing alumina prepared by silicon source is consistent with the peak shape of boehmite, and the silicon-containing alumina adding sodium metasilicate just occurs SiO at low content
2characteristic peak.And adopt and flow plastic method and also occurred SiO
2characteristic peak.This also shows to adopt this one-tenth gluing method clay material and aluminium oxide particles to combine.By simple adjustment clay addition and Gelation Conditions, the silicon-containing alumina of different silica content can be prepared.Silicon-containing alumina prepared by the present invention is applicable to the carrier component being used as the catalyst such as residuum hydrogenating and metal-eliminating, hydrodesulfurization and hydro-conversion.
Claims (15)
1. a preparation method for the dry glue of silicon-containing alumina, comprising:
(1) clay original soil is mixed with weak acid and dispersant, then hydrothermal treatment consists is carried out, obtained modified clay is through pulverizing and sieving, obtain granularity and be greater than 160 object modified clays, described hydrothermal conditions is as follows: temperature is 400 DEG C ~ 700 DEG C, processing time is 1 ~ 8h, and processing pressure is 0.15 ~ 0.35MPa;
(2) containing the alkaline solution of aluminium with add containing in the acid solution of aluminium the modified clay that step (1) obtains respectively, obtain alkaline slurry and acid slurries, temperature wherein containing the acid solution of aluminium is 50 DEG C ~ 95 DEG C, and the temperature containing the alkaline solution of aluminium is 50 DEG C ~ 95 DEG C
(3) add end water in tank in plastic, then also stream adds the alkaline slurry of step (2) gained and acid slurries, and controlling gelling temperature is 50 DEG C ~ 95 DEG C, and plastic pH value is 7.0 ~ 10.5;
(4) filtered by the slurries of step (4) gained, filter cake obtains the dry glue of silicon-containing alumina after washing, drying.
2. in accordance with the method for claim 1, it is characterized in that in step (2), the temperature containing the acid solution of aluminium is 65 DEG C ~ 90 DEG C, and the temperature containing the alkaline solution of aluminium is 65 DEG C ~ 90 DEG C; Step (3) gelling temperature is 65 DEG C ~ 90 DEG C.
3. in accordance with the method for claim 1, it is characterized in that: through Aging Step after step (3) plastic, described aging temperature is 50 DEG C ~ 95 DEG C, and ageing time is 10 ~ 90 minutes.
4. in accordance with the method for claim 1, it is characterized in that: add organic expanding agent in step (3); Described organic expanding agent is one or more in the condensation product of alkyl phenol and oxirane, polyoxyethylene sorbitol acid anhydride list olein, AEO, polyoxyethylene stearic acid ester, and its consumption is 0.1% ~ 10.0% of the dry glue weight of silicon-containing alumina.
5. in accordance with the method for claim 1, it is characterized in that: step (1) weak acid used be boric acid, acetic acid, citric acid, oxalic acid, tartaric one or more, the concentration of weak acid used is 0.5 ~ 3mol/L; Described dispersant be polyethylene glycol, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polypropylene amine one or more, the consumption of described dispersant is 5% ~ 20% of clay original soil weight, and the consumption of weak acid and dispersant is 0.3 ~ 0.9mL/g clay original soil.
6. in accordance with the method for claim 1, it is characterized in that: step (1) weak acid used is boric acid or acetic acid, and described dispersant is polyethylene glycol or polyvinyl alcohol.
7. in accordance with the method for claim 1, it is characterized in that: the described acid solution containing aluminium is the solution of one or more of aluminum sulfate, aluminum nitrate, aluminium chloride; The described alkaline solution containing aluminium is the solution of sodium metaaluminate, potassium metaaluminate or their mixture.
8. in accordance with the method for claim 1, it is characterized in that: the concentration of the acid solution containing aluminium described in step (2) is 20 ~ 50gAl
2o
3/ L, the concentration containing the alkaline solution of aluminium is 40 ~ 100gAl
2o
3/ L.
9. according to the method described in claim 1 or 8, it is characterized in that: in step (2), the alkaline solution added containing aluminium is 4:6 ~ 6:4 with the mass ratio of modified clay in the acid solution containing aluminium.
10. in accordance with the method for claim 1, it is characterized in that: step (2) differs within 5 DEG C with containing the alkaline solution of aluminium and the gelling temperature of step (3) containing the acid solution of aluminium.
11. in accordance with the method for claim 1, it is characterized in that: in step (2), and the alkaline solution added containing aluminium is 5:5 with the mass ratio of modified clay in the acid solution containing aluminium; The acid solution of step (2) containing aluminium is identical with the gelling temperature of the alkaline solution containing aluminium and step (3); In step (3) plastic process, in plastic slurries, solid-to-liquid ratio is constant, and solid-to-liquid ratio is 40 ~ 70g/L.
12. in accordance with the method for claim 1, it is characterized in that: step (4) described drying condition: 100 DEG C ~ 150 DEG C dryings 2 ~ 6 hours.
13. in accordance with the method for claim 1, it is characterized in that: described clay be kaolin, imvite, diatomite, attapulgite one or more.
14. in accordance with the method for claim 1, it is characterized in that: the dry glue of described silicon-containing alumina was through 500 DEG C ~ 950 DEG C roastings 2 ~ 6 hours, and in gained silicon-containing alumina, the content of silica is 1wt% ~ 80wt%.
15. in accordance with the method for claim 14, it is characterized in that the content of silica in gained silicon-containing alumina is 1wt% ~ 60wt%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0283815A1 (en) * | 1987-03-11 | 1988-09-28 | Phillips Petroleum Company | Silica-modified alumina |
| CN102029192A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Silicon-containing alumina and preparation method thereof |
| CN102091609A (en) * | 2010-12-03 | 2011-06-15 | 于向真 | Modified clay new material and preparation method thereof |
-
2012
- 2012-10-24 CN CN201210409222.XA patent/CN103769229B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0283815A1 (en) * | 1987-03-11 | 1988-09-28 | Phillips Petroleum Company | Silica-modified alumina |
| CN102029192A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Silicon-containing alumina and preparation method thereof |
| CN102091609A (en) * | 2010-12-03 | 2011-06-15 | 于向真 | Modified clay new material and preparation method thereof |
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