CN103769229A - Method for preparing silicon-containing alumina dry gel - Google Patents
Method for preparing silicon-containing alumina dry gel Download PDFInfo
- Publication number
- CN103769229A CN103769229A CN201210409222.XA CN201210409222A CN103769229A CN 103769229 A CN103769229 A CN 103769229A CN 201210409222 A CN201210409222 A CN 201210409222A CN 103769229 A CN103769229 A CN 103769229A
- Authority
- CN
- China
- Prior art keywords
- aluminium
- acid
- silicon
- accordance
- containing alumina
- 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.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing silicon-containing alumina dry gel. The preparation method comprises the following steps: mixing original clay with a weak acid and a dispersant, then carrying out a hydrothermal treatment, grinding, sieving so as to obtain modified clay with a particle size larger than 160 meshes; then separately adding the modified clay into an aluminum-containing alkaline solution and an aluminum-containing acidic solution, carrying out a parallel-flow gel-forming treatment under a proper condition, filtering, water washing and drying so as to obtain the silicon-containing alumina dry gel. The preparation method can organically combine clay and the generated alumina particles, and adjusts the pore structure and acidity of the silicon-containing alumina so as to further obtain silicon-containing alumina which has the advantages of uniform particle size and concentrated pore distribution. The obtained silicon-containing alumina dry gel is suitable for being used as a carrier component of a catalyst for hydro-demetallization, hydro-desulfurization, or hydro-conversion of heavy oil or residual oil.
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 of the dry glue of silicon-containing alumina that is applicable to heavy oil or catalyst for hydrotreatment of residual oil carrier material.
Background technology
In the preparation process of petroleum refining used catalyst, conventionally adopt aluminium oxide or silicon-containing alumina as carrier.Independent SiO
2only have weak acidity, the acidity of aluminium oxide is not strong yet, and both mutually combine and show very strong acidity.Much research shows, adds appropriate silica can improve acidity, the specific area of aluminium oxide in aluminium oxide, is conducive to polymerization and hydrogenation reaction.And that silicon-containing alumina has advantages of is unique, 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 has described a kind of preparation method of silicon-containing alumina, take aluminum nitrate and sodium aluminate as raw material, adopt pH value to swing between 2 ~ 10, in the false colloidal sol of the aluminium hydroxide obtaining, add sodium metasilicate, after washing, dry, roasting, obtain silicon-containing alumina, its silicone content is 1 ~ 30%, optimum 3-15%.The method preparation process is too complicated, and select sodium metasilicate is silicon source simultaneously, guarantee to have compared with low sodium content in product, and washing process can produce a large amount of waste water, to environment.
USP7186757 has proposed a kind of method of preparing silicon-containing alumina, is that wherein silicon source is sodium metasilicate by adopting the co-precipitation of two kinds of gel mechanical mixture of Si-Al 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, in conjunction with a little less than, is silicon source owing to selecting sodium metasilicate, guarantee to have compared with low sodium content in product, and 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, in plastic and ageing process, add successively a certain amount of sodium metasilicate, 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 has described a kind of preparation method of cracking catalyst for petroleum hydrocarbon, it be by clay slurry with after acid treatment, add boehmite, water glass solution, add aluminium colloidal sol, then add molecular sieve pulp, spraying is 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 larger, is not suitable for 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 further obtain particle evenly, pore distribution concentration silicon-containing alumina.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) clay original soil is mixed with weak acid and dispersant, then carry out hydrothermal treatment consists, the modified clay making, through pulverizing and sieving, obtains granularity and is greater than 160 object modified clays;
(2) modified clay step (1) being obtained joins respectively containing the alkaline solution of aluminium with containing in the acid solution of aluminium, obtain alkaline slurry and acid slurries, wherein, containing at least 50 ℃ of the temperature of the acid solution of aluminium, be generally 50 ℃ ~ 95 ℃, preferably 60 ℃ ~ 95 ℃, more preferably 65 ℃ ~ 90 ℃, containing at least 50 ℃ of the temperature of the alkaline solution of aluminium, be generally 50 ℃ ~ 95 ℃, preferably 60 ℃ ~ 95 ℃, more preferably 65 ℃ ~ 90 ℃
(3) in plastic cans, add end water, then and stream add alkaline slurry and the acid slurries of step (2) gained, control at least 50 ℃ of plastic temperature, be generally 50 ℃ ~ 95 ℃, preferably 60 ℃ ~ 95 ℃, more preferably 65 ℃ ~ 90 ℃, controlling plastic pH value is 7.0 ~ 10.5, preferably 7.0 ~ 9.5;
(4) slurries of step (4) gained are filtered, filter cake obtains the dry glue of silicon-containing alumina after washing, being dried.
In the inventive method, after step (3) plastic preferably through aging step.Described aging referring to makes solution keep the regular hour under stirring or inactive state.At least 50 ℃ of aging temperatures, are generally 50 ℃ ~ 95 ℃, and preferably 60 ℃ ~ 95 ℃, more preferably 65 ℃ ~ 90 ℃.Ageing time is below 90 minutes, is generally 10 ~ 90 minutes, preferably below 60 minutes, and more preferably 10 ~ 40 minutes.
In the inventive method, preferably can be according to product property in step (3) need to add organic expanding agent.Described organic expanding agent is one or more in the condensation product, polyoxyethylene sorbitol acid anhydride list olein, AEO, polyoxyethylene stearic acid ester of alkyl phenol and oxirane, 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 preferred polyethylene glycol or polyvinyl alcohol.The consumption of described dispersant is 5% ~ 20% of clay original soil weight.General every gram of clay original soil adds weak acid and disperses dosage to be less than 1mL, and preferably the addition of weak acid and dispersant is 0.3 ~ 0.9 mL/g clay original soil.Described hydrothermal treatment consists condition is as follows: temperature is 400 ℃ ~ 700 ℃, 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), adding containing the alkaline solution of aluminium is 4:6 ~ 6:4 with the mass ratio that contains modified clay in the acid solution of 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.The concentration that contains the acid solution of aluminium is 20 ~ 50gAl
2o
3/ L, the described alkaline solution containing aluminium is alkali-metal meta-aluminate solution, preferably sodium metaaluminate, potassium metaaluminate or their mixture, more preferred sodium metaaluminate, the concentration that contains the alkaline solution of aluminium is 40 ~ 100gAl
2o
3/ L.
In the inventive method, preferably differ in 5 ℃ with containing the alkaline solution of aluminium and the plastic temperature of step (3) containing the acid solution of aluminium, 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.Can in plastic cans, suitably add dilution as required, such as water.
In the inventive method, the described drying condition of step (4): 100 ℃ ~ 150 ℃ are dried 2 ~ 6 hours, preferably 110 ℃ ~ 130 ℃, 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 ℃ ~ 950 ℃ roastings 2 ~ 6 hours, the character of gained silicon-containing alumina is as follows: the content of silica is 1wt% ~ 80wt%, preferably 1wt% ~ 60wt%, pore volume is 0.35 ~ 1.10mL/g, 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 below 20% of total pore volume, and the pore volume in the hole of bore dia > 15nm accounts for the more than 30% of total pore volume.
Mesoporous property of the present invention and specific surface are to adopt the analysis of low temperature liquid nitrogen absorption method, and silica content is to adopt metric measurement, and siliceous structure of similar to thin diaspore adopts XRD to characterize.Meleic acid amount is to adopt infrared spectrometer to record, and the adsorbent that uses is pyridine.
The invention has the advantages that: in the dry glue of prepared silicon-containing alumina the content of silica regulate simple, even and if silicone content is high more also can not produce a large amount of waste water.After the present invention adopts raw clay and weak acid and dispersant, water heat-treating methods obtains modified clay, pore volume, surface area and the acidity of this modified clay all have greatly improved, using this modified clay as silicon source, add respectively containing the acid solution of aluminium with containing in the alkaline solution of aluminium, modified clay further reacts respectively with containing the acid solution of aluminium with containing the alkaline solution of aluminium at a certain temperature, to the further modification of clay.Then adopt and flow plastic method plastic, thereby combination again after making in clay silicon and aluminium dissolve, introduce in this way clay and can make the aluminium oxide particles of clay and generation organically combine, regulate the pore structure of silicon-containing alumina and the acidity of silicon-containing alumina.Plastic reaction be preferably in equitemperature, etc. pH value and etc. carry out under solids content condition, the solid product particle that makes like this reaction generate 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 aluminas.
The specific embodiment
Below by further statement technical characterictic of the present invention of embodiment, but be not limited to embodiment.Wt% is mass fraction.
Embodiment 1
Kaolin original soil 100g is fully mixed with 2.0mol/L acetic acid 50mL and the water-soluble solution of 50mL 10g polyglycol solution, carry out modification in hydrothermal treatment device, hydrothermal treatment consists temperature is 600 ℃, processes 4h, hydrothermal treatment consists pressure 0.25MPa.After kaolin after treatment is cooling, pulverized collect after 160 mesh sieve stand-by.
Preparation sodium aluminate solution concentration is 80gAl
2o
3/ L amounts to 0.7L, be heated to 80 ℃ stand-by, aluminum sulfate solution concentration is 20gAl
2o
3/ L amounts to 2L, be heated to 80 ℃ stand-by.
In plastic cans, add 1.5L distilled water, be heated to 80 ℃.The modified kaolin respectively taking respectively after 5g sieves is put in sodium aluminate solution and aluminum sulfate solution, and stream adds above-mentioned two kinds of slurries, keeping pH value is 8.5, be that 50g/L is constant by solid-to-liquid ratio in plastic cans, calculating stream add the time of water, and stream adds 1.0L distilled water, in plastic process, temperature remains on 80 ℃.After cemented into bundles, enter the ageing step, ageing time 50min, 80 ℃ of aging temperatures.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, 110 ℃ dry 5 hours, obtain the dry glue of silicon-containing alumina, 650 ℃ 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 2.0mol/L acetic acid 150mL and the water-soluble 40g polyethylene glycol of 100g, carry out modification in hydrothermal treatment device, hydrothermal treatment consists temperature is 700 ℃, hydrothermal treatment consists pressure 0.30MPa, processing time 4h.After diatomite after treatment is cooling, pulverized collect after 160 mesh sieve stand-by.
Preparation sodium aluminate solution concentration is 50gAl
2o
3/ L amounts to 1.8L, be heated to 70 ℃ stand-by, aluminum sulfate solution concentration is 30gAl
2o
3/ L amounts to 1.0L, be heated to 70 ℃ stand-by.
In plastic cans, add 2.0L distilled water, be heated to 70 ℃.The modification infusorial earth respectively taking respectively after 150g sieves is put in sodium aluminate solution and aluminum sulfate solution, and stream adds above-mentioned two kinds of slurries, keeping pH value is 7.0, be that 40g/L is constant by solid-to-liquid ratio in plastic cans, calculating stream add the time of water, and stream adds 2.2L distilled water, in plastic process, temperature remains on 70 ℃.After cemented into bundles, add condensation product (OP-20) the 134mL(content 250g/L of organic expanding agent alkyl phenol and oxirane, calculate by the 8wt% of solids content).Enter the ageing step, ageing time 50min, 70 ℃ of aging temperatures.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, 100 ℃ dry 5 hours, obtain the dry glue of silicon-containing alumina, 750 ℃ 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 3.0mol/L acetic acid 250mL and the water-soluble 40g polyethylene glycol of 100mL, in hydrothermal treatment device, carry out modification, hydrothermal treatment consists temperature is 500 ℃, hydrothermal treatment consists pressure 0.30MPa, processing time 4h.After mixed material after treatment is cooling, pulverized collect after 160 mesh sieve stand-by.
Preparation sodium aluminate solution concentration is 55gAl
2o
3/ L amounts to 1.8L, be heated to 80 ℃ stand-by, aluminum sulfate solution concentration is 20gAl
2o
3/ L amounts to 1.3L, be heated to 80 ℃ stand-by.
In plastic cans, add 0.7L distilled water, be heated to 80 ℃.The modification material respectively taking respectively after 180g sieves is put in aluminum sulfate solution and sodium aluminate solution, and stream adds above-mentioned two kinds of slurries, keeping pH value is 8.0, be that 50g/L is constant by solid-to-liquid ratio in plastic cans, calculating stream add the time of water, and stream adds 1.8L distilled water, in plastic process, temperature remains on 80 ℃.After cemented into bundles, add condensation product (OP-20) the 152mL(content 250g/L of organic expanding agent alkyl phenol and oxirane, calculate by the 8wt% of solids content).Enter the ageing step, ageing time 30min, 80 ℃ of aging temperatures.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, 110 ℃ dry 4 hours, obtain the dry glue of silicon-containing alumina, 750 ℃ 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 ℃ stand-by, aluminum sulfate solution concentration is 20gAl
2o
3/ L amounts to 2L, be heated to 80 ℃ stand-by.
In plastic cans, add 2.5L distilled water to be heated to 80 ℃.The sodium aluminate solution preparing and aluminum sulfate solution stream are joined in plastic cans, keep 80 ℃ of plastic temperature, plastic pH value 8.5.After cemented into bundles, add waterglass 18.5g(SiO
2content 26wt%, calculates by solids content 5wt%), then enter the ageing step, ageing time 50min, 80 ℃ of aging temperatures.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, 110 ℃ dry 5 hours, obtain the dry glue of silicon-containing alumina, 650 ℃ 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 ℃ stand-by, aluminum sulfate solution concentration is 20gAl
2o
3/ L amounts to 2L, be heated to 80 ℃ stand-by.
In plastic cans, add the modified kaolin 10g after sieving in 2.5L distilled water and embodiment 1, be heated to 80 ℃.And stream adds sodium aluminate solution and aluminum sulfate solution, keeping pH value is 8.5, and in plastic process, temperature remains on 80 ℃.After cemented into bundles, enter the ageing step, ageing time 50min, 80 ℃ of aging temperatures.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, 110 ℃ dry 5 hours, obtain the dry glue of silicon-containing alumina, 650 ℃ of roastings 3 hours, obtain silicon-containing alumina G, wherein SiO
2content be 5wt%.
The physico-chemical property of the silicon-containing alumina that obtained is above listed in to 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: in the time containing close silica in aluminium oxide, in plastic raw material, add clay material be silicon source compared with adding sodium metasilicate, aperture ratio significantly reduces and pore distribution concentration, has also increased the acidity of aluminium oxide simultaneously.As can be seen from Figure 1: adopting clay material is that silicon the source XRD of silicon-containing alumina and the peak shape of boehmite prepared are consistent, and adds the silicon-containing alumina of sodium metasilicate just to occur SiO at low content
2characteristic peak.Also there is SiO and adopt and flow plastic method
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 plastic condition, can prepare the silicon-containing alumina of different silica contents.Silicon-containing alumina prepared by the present invention is applicable to being used as the carrier component of the catalyst such as residuum hydrogenating and metal-eliminating, hydrodesulfurization and hydro-conversion.
Claims (16)
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 carry out hydrothermal treatment consists, the modified clay making, through pulverizing and sieving, obtains granularity and is greater than 160 object modified clays;
(2) containing the alkaline solution of aluminium with containing the modified clay that adds respectively step (1) to obtain in the acid solution of aluminium, obtain alkaline slurry and acid slurries, the temperature that wherein contains the acid solution of aluminium is 50 ℃ ~ 95 ℃, and the temperature that contains the alkaline solution of aluminium is 50 ℃ ~ 95 ℃
(3) in plastic, in tank, add end water, then and stream add alkaline slurry and the acid slurries of step (2) gained, controlling plastic temperature is 50 ℃ ~ 95 ℃, plastic pH value is 7.0 ~ 10.5;
(4) slurries of step (4) gained are filtered, filter cake obtains the dry glue of silicon-containing alumina after washing, being dried.
2. in accordance with the method for claim 1, it is characterized in that in step (2), the temperature that contains the acid solution of aluminium is 65 ℃ ~ 90 ℃, and the temperature that contains the alkaline solution of aluminium is 65 ℃ ~ 90 ℃; Step (3) plastic temperature is 65 ℃ ~ 90 ℃.
3. in accordance with the method for claim 1, it is characterized in that: after step (3) plastic, through aging step, described aging temperature is 50 ℃ ~ 95 ℃, and ageing time is 10 ~ 90 minutes.
4. it is characterized in that in accordance with the method for claim 1: in step (3), add organic expanding agent; Described organic expanding agent is one or more in the condensation product, polyoxyethylene sorbitol acid anhydride list olein, AEO, polyoxyethylene stearic acid ester of alkyl phenol and oxirane, 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 is one or more of polyethylene glycol, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polypropylene amine, and the consumption of described dispersant is 5% ~ 20% of clay original soil weight, and the consumption of weak acid and dispersant is 0.3 ~ 0.9 mL/g clay original soil.
6. in accordance with the method for claim 1, it is characterized in that: described hydrothermal treatment consists condition is as follows: temperature is 400 ℃ ~ 700 ℃, and the processing time is 1～8h, and processing pressure is 0.15～0.35MPa.
7. 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.
8. it is characterized in that in accordance with the method for claim 1: the described acid solution containing aluminium is one or more solution of aluminum sulfate, aluminum nitrate, aluminium chloride; The described alkaline solution containing aluminium is the solution of sodium metaaluminate, potassium metaaluminate or their mixture.
9. it is characterized in that in accordance with the method for claim 1: the concentration of the acid solution containing aluminium described in step (2) is 20 ~ 50gAl
2o
3/ L, the concentration that contains the alkaline solution of aluminium is 40 ~ 100gAl
2o
3/ L.
10. according to the method described in claim 1 or 9, it is characterized in that: in step (2), adding containing the alkaline solution of aluminium is 4:6 ~ 6:4 with the mass ratio that contains modified clay in the acid solution of aluminium.
11. in accordance with the method for claim 1, it is characterized in that: step (2) differs in 5 ℃ containing the acid solution of aluminium and containing the alkaline solution of aluminium and the plastic temperature of step (3).
12. in accordance with the method for claim 1, it is characterized in that: in step (2), adding containing the alkaline solution of aluminium is 5:5 with the mass ratio that contains modified clay in the acid solution of aluminium; Step (2) contains the acid solution of aluminium with identical containing the alkaline solution of aluminium and the plastic temperature of 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.
13. in accordance with the method for claim 1, it is characterized in that: the described drying condition of step (4): 100 ℃ ~ 150 ℃ are dried 2 ~ 6 hours.
14. in accordance with the method for claim 1, it is characterized in that: described clay is one or more of kaolin, imvite, diatomite, attapulgite.
15. in accordance with the method for claim 1, it is characterized in that: the dry glue of described silicon-containing alumina was through 500 ℃ ~ 950 ℃ roastings 2 ~ 6 hours, and in gained silicon-containing alumina, the content of silica is 1wt% ~ 80wt%.
16. in accordance with the method for claim 15, and the content that it is characterized in that silica in gained silicon-containing alumina is 1wt% ~ 60wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409222.XA CN103769229B (en) | 2012-10-24 | 2012-10-24 | A kind of method preparing the dry glue of silicon-containing alumina |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409222.XA CN103769229B (en) | 2012-10-24 | 2012-10-24 | A kind of method preparing the dry glue of silicon-containing alumina |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769229A true CN103769229A (en) | 2014-05-07 |
| CN103769229B CN103769229B (en) | 2016-02-03 |
Family
ID=50562262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210409222.XA Active CN103769229B (en) | 2012-10-24 | 2012-10-24 | A kind of method preparing the dry glue of silicon-containing alumina |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103769229B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471642A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Phosphorus and boron-containing hydrodesilicification catalyst, preparation method thereof and hydrodesilicification method |
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471642A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Phosphorus and boron-containing hydrodesilicification catalyst, preparation method thereof and hydrodesilicification method |
| CN114471642B (en) * | 2020-10-27 | 2023-07-14 | 中国石油化工股份有限公司 | Hydrodesilicification catalyst containing phosphorus and boron, preparation method thereof and hydrodesilicification method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103769229B (en) | 2016-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102029192B (en) | Silicon-containing alumina and preparation method thereof | |
| CN103769122B (en) | A kind of method preparing hydrotreating catalyst | |
| CN103769069A (en) | Preparation method of alumina dry glue containing silicon | |
| CN105056928B (en) | A kind of preparation method of controllable hole structure sial composite oxides | |
| CN106809855B (en) | A kind of porous material and preparation method thereof | |
| CN103769232B (en) | The preparation method of the dry glue of a kind of silicon-containing alumina | |
| CN102257121A (en) | Diatomaceous earth products, processes for preparing them, and methods of their use | |
| CN106669778B (en) | Light oil type hydrocracking catalyst and preparation method thereof | |
| CN105709789B (en) | A kind of hydrocracking heavy oil catalyst and its preparation method and application | |
| CN104549540A (en) | Preparation method of macroporous amorphous silica-alumina carrier | |
| CN103769121A (en) | Preparation method of catalyst for hydro-treatment | |
| CN103769229B (en) | A kind of method preparing the dry glue of silicon-containing alumina | |
| CN103769071B (en) | Prepare the method for the dry glue of silicon-containing alumina | |
| CN107286987B (en) | A kind of group technology handling poor ignition quality fuel | |
| CN106587085B (en) | The preparation method of large aperture Alusil | |
| CN108940351A (en) | A kind of preparation method of catalysis material | |
| CN106809854B (en) | A kind of preparation method of porous material | |
| CN105709713B (en) | A kind of high silicon aluminium dry glue and preparation method thereof | |
| CN104549538B (en) | A kind of preparation method of amorphous silicon alumina supporter | |
| CN108927123A (en) | A kind of porous catalyst material and preparation method thereof | |
| CN1331605C (en) | Alumina support containing silicon and titanium and preparation method thereof | |
| CN103769123B (en) | The method preparing hydrotreating catalyst | |
| CN103769231B (en) | A kind of preparation method of silicon-containing alumina carrier | |
| CN107286988B (en) | A kind of process handling poor ignition quality fuel | |
| CN104324711A (en) | Preparation method of serpentine supported type TiO2 photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |