CN105056928B - A kind of preparation method of controllable hole structure sial composite oxides - Google Patents
A kind of preparation method of controllable hole structure sial composite oxides Download PDFInfo
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- CN105056928B CN105056928B CN201510574333.XA CN201510574333A CN105056928B CN 105056928 B CN105056928 B CN 105056928B CN 201510574333 A CN201510574333 A CN 201510574333A CN 105056928 B CN105056928 B CN 105056928B
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Abstract
The present invention is a kind of preparation method of controllable hole structure sial composite oxides, and its feature includes step：Aluminum source compound and silicon source compound are subjected to neutralization plastic at ambient pressure, autoclave is transferred to after cemented into bundles, controls certain condition to carry out hydrothermal aging, then separation of solid and liquid, is washed, dries, obtains the sial composite oxide powder of different pore size.Compared with prior art, this method sial composite oxides are using neutralization hydro-thermal process, make the full and uniform mixing of reactant, it ensure that silicon atom effectively interacts with aluminium atom, by controlling different hydrothermal conditions and hydro-thermal time, adjust the syneresis depth of silica-alumina gel, obtain the gel of different frame strengths, so as to be significantly improved in the pore structure of interior regulation Alusil in a big way, the effective hole proportion of sial composite oxides of preparation, 80% hole integrated distribution is in the range of ± 2nm.
Description
Technical field：
The invention belongs to field of inorganic material preparing technology, is related to a kind of preparation side of controllable hole structure sial composite oxides
Method, more particularly to a kind of method that adjustable, pore distribution concentration the sial composite oxides in aperture are prepared by neutralization-hydro-thermal reaction.
Background of invention：
Carrier or active component of the sial composite oxides as loaded catalyst, are widely used to each catalytic field
In, especially it is widely applied in the catalytic cracking of oil refining industry and hydrocracking technology field.With petroleum resources day
Beneficial in poor quality and heaviness, a large amount of organo-metallic compounds and asphalitine be present in feedstock oil, it is desirable to various petroleum refinements catalysis
Agent carrier has sufficiently large aperture to be diffused, and prevents or slow down poisoning or the inactivation of catalyst
Sial composite oxides have larger pore volume, not only increase catalyst coking or anti-carbon performance, Jin Eryan
The service life of long catalyst, also help catalyst regeneration.Sial composite oxides also have big ratio surface simultaneously, make work
Property component it is preferably scattered so that it is guaranteed that catalyst has high catalytic activity.But increasingly becoming more meticulous with PETROLEUM PROCESSING,
Sial composite oxide carrier with Large ratio surface and pore volume is not the requirement that can meet different fractions oil processing, therefore
Propose the concept in effective hole.For specific distillate, the hole with specific pore size distribution is considered as effective hole, for aperture
Too small reactant can not by or the too big reactant in aperture be not enough to rest on the hole to react in hole and be referred to as invalid hole, this
Require sial composite oxide carrier will also be with narrow pore size distribution with large surface and while pore volume.
At present, the method for industrial production sial composite oxides has a variety of, as aluminate or the aluminium salt precipitation method, aluminium salt neutralize
Method, carbonizatin method and aluminium alcoholates Hydrolyze method etc..
CN 1597093A disclose a kind of method that carbonizatin method prepares sial composite oxides, are into sodium aluminate solution
Add part and contain sodium silicate solution, then pass to CO2 gases, after certain time, add remaining sodium silicate solution.It is prepared by this method
Sial composite oxides there is suitable ratio surface, pore volume and suitable acidity.But the use of carbonizatin method is by equipment, original
The factors such as material and plastic pH tuning ranges are small limit, it is impossible to meet raising and the work of sial combined oxidation physical performance well
The requirement that industry is promoted.
GB2166971 discloses a kind of preparation method of sial composite oxides, the method precipitated simultaneously using sial, first
Basic aluminium salt is mixed with sodium metasilicate at a high ph, then again with reacting aluminum sulfate.Sial combined oxidation prepared by this method
Thing is all smaller than surface and pore volume.
CN 1210755A disclose a kind of sial composite oxides and preparation method thereof, using cocurrent fixed pH method.The hair
Bright sial composite oxides have larger pore volume and specific surface area, but aperture 4-15nm pore volume only accounts for total pore volume
50%.
It is various improve, the modified methods for preparing sial composite oxides also have been reported that in prior art,
CN1210755A discloses the sial composite oxides that sial is co-precipitated and uses organic-silicon-modified method to prepare high silicon content；
CN 1210755A disclose a kind of preparation method of sial composite oxides, alkaline first using the preparation method of silicon after first aluminium
Precipitating reagent, into aluminum oxide, then introduces silicon source with acid Mr. silicon source.These preparation methods are uneven there is Distribution of silicon and aluminium, hole
Footpath is small or the shortcomings that pore-size distribution is not concentrated.
The content of the invention：
For the shortcomings of the prior art, concentrated it is an object of the invention to provide a kind of pore-size distribution, be big
The preparation method of the sial composite oxides of surface area and big pore volume.This method preparation process is simple, and cost is cheap, is adapted to industry
Metaplasia is produced.
The present invention is a kind of preparation method of controllable hole structure sial composite oxides；It is characterized in that：Including following step
Suddenly：
1) aluminum source compound and silicon source compound are subjected to neutralization plastic in atmospheric conditions, the temperature for controlling reaction is
20-80 DEG C, pH value 4.0-10.0；
2) slurry obtained by step 1) is added into reactor and carries out 0.5~10h of hydro-thermal reaction in 100~200 DEG C；
3) after reaction terminates, slurries obtained by step 2) is subjected to separation of solid and liquid, washing, obtain the product filter of imurity-removal
Cake；
4) by filtration cakes torrefaction, crushing obtained by step 3), sial composite oxide powder is obtained.
According to preparation method of the present invention, it is characterised in that：Aluminum source compound and silicon source wherein described in step 1)
In compound and plastic is that silicon source compound be bottom liquid, in addition aluminum source compound and plastic, or silicon source compound and aluminium
Source compound cocurrent plastic；
Aluminum source compound described in step 1) with plastic in silicon source compound with including acid silicon source and being neutralized with alkaline silicon source
In plastic, or alkaline silicon source and acid silicon source and plastic；
Acid silicon source described in step 1) includes aluminum sulfate, aluminum nitrate or aluminium chloride；Alkaline silicon source include sodium metaaluminate or
Potassium metaaluminate；Silicon source includes waterglass, Ludox；
According to preparation method of the present invention, it is characterised in that：Prepared sial composite oxide powder has such as
Lower property, alumina weight content is in 10%-50%, than surface in 300-500m2/ g, pore volume is in 0.8-1.8ml/g, average hole
Footpath is in 5~20nm, and 80% hole integrated distribution is in the range of ± 2nm.
The present invention uses neutralization-hydro-thermal method, makes the full and uniform mixing of reactant, ensure that silicon atom is effective with aluminium atom
Interaction.
The present invention uses neutralization-hydro-thermal method, by controlling different hydrothermal conditions and hydro-thermal time, adjusts silica-alumina gel
Syneresis depth, at the same be full of in gel voids sial composite oxides monomer, oligomer, primary granule, small polymerization
Thing is progressively attached on gel skeleton, obtains the gel of different frame strengths, so as in interior regulation Alusil in a big way
Pore structure, it is compound in 5~20nm, amorphous silica-alumina of the 80% hole integrated distribution in the range of ± 2nm that average pore size can be obtained
Oxide, to be directed to different requirements, prepare the sial composite oxide material with different pore size distribution.
It is of the invention to use neutralization-hydro-thermal method, it is main during being somebody's turn to do that perfect particle growth, crystal formation and crystal transfer occurs and coagulates
Glue syneresis etc. changes, and the condition and hydrothermal condition of plastic are neutralized by adjusting, and can control the size, crystalline phase, shape of crystal grain
Looks, so as to form the sial composite oxides of the large surface of pore-size distribution concentration and pore volume.
Sial composite oxides of the present invention are not only that reactant provides enough passages, are advantageous to reactant and product
Disengaging, greatly improve the active ingredient of carrier, in addition with narrow pore-size distribution, improve effective hole of catalyst, make
Catalyst not only has suitable activity, with more high selectivity.
Sial composite oxides of the present invention use neutralization-hydro-thermal process, avoid component volatilization, are advantageous to improve the pure of product
Degree and environmental protection.
Embodiment：
Embodiment 1
Take SiO2Content is that 55-150g/L water glass solution 1.5L is placed in plastic cans, and certain flow rate adds Al2O3Contain
It is that 8.0-9.0 stops feeding to measure as 50-90g/L aluminum sulfate solutions to pH value, and after cemented into bundles, above-mentioned slurries are added into autoclave
In, 120 DEG C are warming up to, after keeping 2h, reaction to terminate, separation of solid and liquid, washing, obtains the product cake of imurity-removal, filter cake is done
Dry, crushing, obtains sial composite oxide powder.
Embodiment 2
Take SiO2Content is that 55-150g/L acidic silicasol solution 1.5L is placed in plastic cans, and certain flow rate adds
Al2O3Content is that 50-90g/L sodium aluminate solutions to pH value is that 7.0-8.0 stops feeding, and after cemented into bundles, above-mentioned slurries are added
Enter in autoclave, be warming up to 140 DEG C, keep 2h.After reaction terminates, separation of solid and liquid, washing, the product filter of imurity-removal is obtained
Cake, filtration cakes torrefaction, crushing, obtain sial composite oxide powder.
Embodiment 3
Take SiO2Content is that 55-150g/L alkaline silica sol solution 1.5L is placed in plastic cans, and certain flow rate adds
Al2O3Content is that 50-90g/L aluminum sulfate solutions to pH value is that 6.0-7.0 stops feeding, and after cemented into bundles, above-mentioned slurries are added
In autoclave, 160 DEG C are warming up to, keeps 10h.After reaction terminates, separation of solid and liquid, washing, the product cake of imurity-removal is obtained,
Filtration cakes torrefaction, crushing, obtain sial composite oxide powder.
Embodiment 4
Take SiO2Content is that 55-150g/L water glass solution 1.5L is placed in plastic cans, and certain flow rate adds Al2O3Contain
It is 8.0-9.0 to measure as 50-90g/L aluminum nitrate solutions to pH value, stops feeding, and after cemented into bundles, above-mentioned slurries are added into high pressure
In kettle, 180 DEG C are warming up to, keeps 1h.After reaction terminates, separation of solid and liquid, washing, the product cake of imurity-removal, filter cake are obtained
Dry, crush, obtain sial composite oxide powder.
Embodiment 5
Take SiO2Content is that 55-150g/L water glass solution 1.5L is placed in plastic cans, and certain flow rate adds Al2O3Contain
It is 8.0-9.0 to measure as 50-90g/L liquor alumini chloridis to pH value, stops feeding, and after cemented into bundles, above-mentioned slurries are added into high pressure
In kettle, 200 DEG C are warming up to, keeps 0.5h.After reaction terminates, separation of solid and liquid, washing, the product cake of imurity-removal is obtained, filtered
Biscuit is dry, crushes, and obtains sial composite oxide powder.
Comparative example 1
Take SiO2Content is that 55-150g/L water glass solution 1.5L is placed in plastic cans, and certain flow rate adds Al2O3Contain
It is 8.0-9.0 to measure as 50-90g/L aluminum sulfate solutions to pH value, stops feeding, after cemented into bundles, by above-mentioned slurries at ambient pressure,
90 DEG C are warming up to, keeps 2h.After reaction terminates, separation of solid and liquid, washing, the product cake of imurity-removal, filtration cakes torrefaction, powder are obtained
It is broken, obtain sial composite oxide powder.
Comparative example 2
Take SiO2Content is that 55-150g/L acidic silicasol solution 1.5L is placed in plastic cans, and certain flow rate adds
Al2O3Content is that 50-90g/L sodium aluminate solutions to pH value is 7.0-8.0, stops feeding, after cemented into bundles, by above-mentioned slurries
At ambient pressure, 80 DEG C are warming up to, keeps 8h.After reaction terminates, separation of solid and liquid, washing, the product cake of imurity-removal is obtained, filtered
Biscuit is dry, crushes, and obtains sial composite oxide powder.
The physico-chemical property of each embodiment product of table 1
Claims (3)
- A kind of 1. preparation method of controllable hole structure sial composite oxides；It is characterized in that：Comprise the following steps：1) aluminum source compound and silicon source compound are subjected to neutralization plastic in atmospheric conditions, the temperature for controlling reaction is 20-80 DEG C, pH value 4.0-10.0；2) slurry obtained by step 1) is added into reactor and carries out 0.5~10h of hydro-thermal reaction in 160~200 DEG C；3) after reaction terminates, slurries obtained by step 2) is subjected to separation of solid and liquid, washing, obtain the product cake of imurity-removal；4) by filtration cakes torrefaction, crushing obtained by step 3), sial composite oxide powder is obtained；The average pore size of wherein described sial composite oxide powder in 5-20nm, and 80% hole integrated distribution in ± 2nm In the range of.
- 2. according to the preparation method described in claim 1, it is characterised in that：Aluminum source compound and silicon source wherein described in step 1) In compound and plastic is that silicon source compound be bottom liquid, in addition aluminum source compound and plastic, or silicon source compound and aluminium Source compound cocurrent plastic；In aluminum source compound and silicon source compound described in step 1) and plastic includes in acid silicon source and alkaline silicon source and plastic, Or in alkaline silicon source and acid silicon source and plastic；Acid silicon source described in step 1) includes aluminum sulfate, aluminum nitrate or aluminium chloride；Alkaline silicon source includes sodium metaaluminate or inclined aluminium Sour potassium；Silicon source includes waterglass, Ludox.
- 3. according to the preparation method described in claim 1, it is characterised in that：Prepared sial composite oxide powder has such as Lower property, alumina weight content is in 10%-50%, than surface in 300-500m2/ g, pore volume is in 0.8-1.8ml/g.
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| CN106807351B (en) * | 2015-12-01 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of preparation method of mesoporous activated material |
| CN106582597B (en) * | 2016-12-09 | 2019-05-07 | 中国石油天然气股份有限公司 | A kind of Si modification aluminium oxide and its preparation method and application |
| CN108940251B (en) * | 2017-05-26 | 2021-04-06 | 中国石油化工股份有限公司 | Preparation method of active catalytic material |
| CN108940351B (en) * | 2017-05-26 | 2021-04-06 | 中国石油化工股份有限公司 | Preparation method of catalytic material |
| CN110759370A (en) * | 2019-11-27 | 2020-02-07 | 于向真 | Preparation method of active silicon-aluminum powder |
| CN114749193B (en) * | 2021-01-11 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst for producing low-sulfur ship combustion and preparation method thereof |
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| CN114749195B (en) * | 2021-01-11 | 2023-09-01 | 中国石油化工股份有限公司 | Crude oil hydrocracking catalyst and preparation method thereof |
| CN114749170B (en) * | 2021-01-11 | 2023-09-01 | 中国石油化工股份有限公司 | Silicon-aluminum particle aggregate, and manufacturing method and application thereof |
| CN113184860A (en) * | 2021-05-18 | 2021-07-30 | 济南大学 | Preparation method of pore structure controllable silica-alumina gel |
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| US4758338A (en) * | 1986-12-22 | 1988-07-19 | Johnson Sr Lester L | Oil refiner and filter compacting system |
| CN1123383C (en) * | 1997-09-10 | 2003-10-08 | 中国石油化工集团公司 | Amorphous silica-alumina and its preparing method |
| CN1261217C (en) * | 2003-06-30 | 2006-06-28 | 中国石油化工股份有限公司 | Process for preparing mesoporous Si-Al material and its preparing process |
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| JP2010155759A (en) * | 2008-12-27 | 2010-07-15 | Yoshihiro Sugi | Method for synthesizing mesoporous aluminosilicate |
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| CN103100407B (en) * | 2011-11-11 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst containing molecular sieve and amorphous silica-alumina |
| CN103100436B (en) * | 2011-11-11 | 2014-12-31 | 中国石油化工股份有限公司 | Preparation method of catalyst carrier dry gel powder |
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Address after: 100010 No. 25 North Main Street, Dongcheng District, Beijing, Chaoyangmen Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 No. 25 North Main Street, Dongcheng District, Beijing, Chaoyangmen Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |