CN104556068B - Porous silica and preparation method thereof - Google Patents

Porous silica and preparation method thereof Download PDF

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CN104556068B
CN104556068B CN201310503640.XA CN201310503640A CN104556068B CN 104556068 B CN104556068 B CN 104556068B CN 201310503640 A CN201310503640 A CN 201310503640A CN 104556068 B CN104556068 B CN 104556068B
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porous silica
inorganic base
preparation
silica
white carbon
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CN104556068A (en
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范峰
凌凤香
王少军
张会成
陈晓刚
杨春雁
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention provides porous silica and a preparation method thereof. According to the porous silica, the composition is amorphous silica, the size of particles is 10-20 microns, the particles consist of 30-60nm silica primary particles, the specific surface area is 50-150m<2>/g, and the porous silica has the characteristic of graded pore distribution and has the pore size of 10-500nm. The preparation method of the porous silica comprises the following steps: (1) mixing white carbon black and distilled water, and then, stirring under ultrasonic conditions; (2) adding an inorganic base into the mixture obtained in the step (1) under the condition of stirring until the inorganic base is completely dissolved, and then, drying the mixture; (3) roasting the mixture obtained in the step (2), washing and drying, thereby obtaining the porous silica. According to the method provided by the invention, expensive organic template agents are not used, operating steps are simple and feasible, and the production cost is low.

Description

A kind of porous silica and preparation method thereof
Technical field
The invention belongs to porous inorganic material synthesis field, specifically a kind of porous silica silicon materials and its preparation Method.
Background technology
Porous oxidation silicon materials have wide answering in fields such as catalysis, absorption, separation, biomaterial, energy and environment Use prospect.The technology that at present prepared by porous oxidation silicon materials is highly developed, but also in development, such as meso-porous titanium dioxide Silicon, also referred to as meso-porous molecular sieve material are exactly a study hotspot, and the species prepared also compares many, and such as M41S is serial, SBA15 etc..The synthesis of mesopore molecular sieve needs several materials, wherein surface activity such as surfactant, water, silicon source, acid or alkali Agent is used as the factor that template is most critical.Because the comparison studied is goed deep into, it was also proposed that many theories, such as liquid crystal templated machine Reason, bar-shaped self assembly model, charge matching mechanism, stratiform wrinkle model etc..
In addition with macropore silicon oxide, the synthetically prepared of multistage pore canal silica material also gets most of the attention, and many materials Material is applied in many fields of industry.The equal grain porous silica microsphere of CN102070152 A functionalization and its system Preparation Method and application, disclose a kind of porous silica silicon preparation method.The previously prepared equal grain porous polymer microsphere of the patent, Such as methacrylic acid fat, single polymers of Styrene and its derivatives or copolymer microsphere, and porous polymer microsphere is entered The surface-functionalized process of row, obtains the equal grain porous polymer microsphere of functionalization;(2) functionalization porous polymer microsphere is dispersed in In aqueous solution, it is subsequently adding silica precursor and prepares to form complex microsphere in the middle of silicon dioxide/polymer;(3) by dioxy Complex microsphere adds heat extraction polymer in the middle of SiClx/polymer, obtains equal grain porous silica microsphere;(4) using chemistry examination Agent carries out surface modification to equal grain porous silica microsphere and forms functional group.But the method is expensive organic due to what is used Single polymers of thing template, such as Styrene and its derivatives or copolymer microsphere, and operating procedure is complicated, preparation cost is too high.
" utilizing coal ash for manufacturing for the experiment of porous silica "《Modern geology》(The 4th phases of volume 20 in 2006)Disclose one kind The preparation method of porous silica.The method utilizes phase separation principle, the obtained silicon Jing after sial separation with flyash as raw material Acid gel, is pore creating material from polyvinyl alcohol, and nitric acid is catalyst, prepares a kind of porous silica containing three-level duct. The primary particle of the material is 3 μm or so of microsphere, about 1~2 μm of macropore.But the specific surface of the silicon oxide that the method is obtained Too little, only 12.03 m of product2/ g, application is narrower.
" lignin trimethyl quaternary ammonium salt prepares porous oxidation silicon materials for template "《Beijing Forestry University's journal》(2011 The phase of volume 33 the 4th year)Disclose a kind of preparation method of porous silica.Article with lignin trimethyl quaternary ammonium salt as template, Tetraethyl orthosilicate is silicon source, and using sol-gal process and the roasting demoulding method porous oxidation silicon materials are prepared.The aperture master of the material 2.7~5.6 nm are distributed in, average pore size is 21.4 nm.But the method is preparing template lignin trimethyl quaternary ammonium salt When used the poisonous organic reagent such as a large amount of trimethylamines, epoxychloropropane, preparation cost is high, and severe operational environment.
A kind of macroporous silicon dioxide carriers of CN1339329A and preparation method thereof, disclose a kind of macroporous silicon dioxide carrier And preparation method thereof.The patent is first to dissolve alkali-metal inorganic salt deionized water, is configured to double salt dipping solution;Use again The dipping solution dipping porous matrix that 1st step is obtained, then dry, roasting is obtained macroporous silicon dioxide carrier finished product.The material Average pore size be 30~600nm, but after aperture is more than 50nm, its specific surface area is drastically reduced, and specific surface area is too low.
The preparation method of CN1113923A high porosity silicon dioxide particles, discloses a kind of porous silica and prepares Method.The patent is, with common silica gel as raw material, to corrode silica gel in a certain temperature conditions using soda acid, such as in Fluohydric acid. In 25 degree process 6 hours.The method manufactures the process of secondary pore similar to the post processing of zeolite soda acid, due to being acid and alkali corrosion silica gel Pore-creating, necessarily causes the loss of element silicon, and porosity is higher, and element silicon loss is more, not only causes the waste of raw material, also can Cause serious pollution.
At present, the preparation method of existing porous oxidation silicon materials, mostly using expensive Organic substance as template or Organic additive, and operating procedure also comparison step, these all cause the preparation cost of material too high, hinder such technology Commercial production is moved towards from laboratory.And prior art needs to improve in terms of special material is prepared, such as big in particle diameter The control method of little and pattern control, pore-size distribution and pore size also has huge room for promotion.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of porous silica and preparation method thereof.
The porous silica that the present invention is provided has excellent porous property, and preparation method is simple, low production cost.
The present invention provides a kind of porous silica, with following feature:Amorphous silica is consisted of, granular size is 10~20 μm, granule is made up of the silica primary particles of 30~60nm, and specific surface area is 50~150 m2/ g, with grade Pore size distribution feature, aperture is 10~50nm.
The preparation method of porous silica of the present invention, comprises the following steps:
(1)White carbon is mixed with distilled water, is then stirred under ultrasound condition;
(2)Under agitation, inorganic base is added to into step(1)It is completely dissolved to inorganic base in the mixture for obtaining, Then process is dried to mixture;
(3)Step(2)Gained mixture carries out being porous silica after roasting, washing and dried.
Synthetic method of the invention, wherein step(1)Described in white carbon be general industry commodity, preferred size White carbon less than 60nm.
Step(1)Described in the mass ratio of white carbon and distilled water be 1:100~10:100, preferably 3:100~7: 100。
Step(1)The middle stir process time is 1~10 h, preferably 3~7 h.
Step(2)Described in inorganic base can be one or more in NaOH, KOH, LiOH, preferred NaOH.
Step(2)Described in the mass ratio of white carbon and inorganic base be 40:1~10:1, preferably 30:1~15:1.
Step(2)Described in dried temperature be less than 80 DEG C, preferably smaller than 70 DEG C.
Step(3)Described in sintering temperature be 300~900 DEG C, preferably 500~700 DEG C;Roasting time is 1~15h, excellent Select 3~10h;The washing to be washed with deionized to neutrality, the drying be dried 5 under the conditions of 100~140 DEG C~ 15h。
The porous silica that the present invention is provided is the porous silica with certain pattern, can be used as catalyst carrier, Adsorbent, chromatographic column filler, it is also possible to make the synthesis masterplate of inorganic organic material.
Compared with prior art, porous silica that the present invention is provided and preparation method thereof has advantages below:
(1)The present invention provides porous silica and has unique physicochemical characteristic, and its particle size can be controlled in 10~20 μ M, and even particle size distribution;Pore-size distribution is foramen magnum-mesoporous equally distributed grade hole, and substance diffusion can be excellent.
(2)Porous silica of the present invention and preparation method thereof is simple, and topmost feature is not use costliness poisonous Organic formwork agent or additive, also not with expensive organosilicon as silicon source, so manufacturing cost is low.
(3)It is, with dispersity presence, model to be leaned between granule as the white carbon molecule of raw material in the inventive method De Huali loose absorption is packed together, it is impossible to forms the offspring with definite shape and size, can not form rule Duct then.Jing after the inventive method process, silica particles adsorb alkali in outer surface, chemistry after heat treatment occurs and makees With the active force between molecule is changed into stronger chemical bond from faint Van der Waals force, is formed and has foramen magnum-mesoporous uniform point The grade duct of cloth, and the particle diameter of offspring is in 10~20 μ ms, becomes the poriness silicon oxide of tool certain function Material.
Description of the drawings
The low power SEM photograph of the porous silica of the synthesis of Fig. 1 embodiments 1.
The high power SEM photograph of the porous silica of the synthesis of Fig. 2 embodiments 1.
Specific embodiment
The porous oxidation silicon preparation method of the present invention is described in detail below by specific embodiment, but not office It is limited to embodiment.
Embodiment 1
(1)5 g white carbons are mixed with 100 mL distilled water, the h of stir process 5 under ultrasound condition.
(2)0.25 g sodium hydroxide is added to into step(1)In obtaining mixture, 3 min are stirred;Then in 60 DEG C of bar Drying under part is evaporated moisture.
(3)By step(2)Obtain mixture h of roasting 5 under the conditions of 600 DEG C;Neutrality is washed with distilled water to again, 120 DEG C of h of drying 12, obtain porous silica, and numbering is CL1.
Embodiment 2
(1)4 g white carbons are mixed with 100 mL distilled water, 5.5 h are stirred under ultrasound condition.
(2)0.15 g sodium hydroxide is added to into step(1)In obtaining mixture, 3 min are stirred;Then in 50 DEG C of bar Drying under part is evaporated moisture.
(3)By step(2)Obtain mixture h of roasting 5 under the conditions of 650 DEG C;Neutrality is washed with distilled water to again, 120 DEG C of h of drying 12, obtain porous silica, and numbering is CL2.
Embodiment 3
(1)6 g white carbons are mixed with 80 mL distilled water, 5 h are stirred under ultrasound condition.
(2)0.3 g sodium hydroxide is added to into step(1)In obtaining mixture, 3 min are stirred;Then in 60 DEG C of bar Drying under part is evaporated moisture.
(3)By step(2)Obtain mixture h of roasting 5 under the conditions of 600 DEG C;Neutrality is washed with distilled water to again, 120 DEG C of h of drying 12, obtain porous silica, and numbering is CL3.
Embodiment 4
(1)7 g white carbons are mixed with 100 mL distilled water, 5 h are stirred under ultrasound condition.
(2)0.5 g sodium hydroxide is added to into step(1)In obtaining mixture, 3 min are stirred;Then in 35 DEG C of bar Drying under part is evaporated moisture.
(3)By step(2)Obtain mixture h of roasting 7 under the conditions of 550 DEG C;Neutrality is washed with distilled water to again, 120 DEG C of h of drying 12, obtain porous silica, and numbering is CL4.
Embodiment 5
(1)5.5g white carbons are mixed with 70 mL distilled water, 5 h are stirred under ultrasound condition.
(2)0.55g sodium hydroxide is added to into step(1)In obtaining mixture, 3 min are stirred;Then in 55 DEG C of bar Drying under part is evaporated moisture.
(3)By step(2)Obtain mixture h of roasting 8 under the conditions of 500 DEG C;Neutrality is washed with distilled water to again, 120 DEG C of h of drying 12, obtain porous silica, and numbering is CL5.
Table 1 is embodiment gained sample physico-chemical property

Claims (13)

1. a kind of preparation method of porous silica, the porous silica has following feature:Consist of amorphous titanium dioxide Silicon, granular size is 10~20 μm, and granule is made up of the silica primary particles of 30~60nm, and specific surface area is 50~150 m2/ g, with grade pore size distribution feature, aperture is 10~500 nm, and the preparation method is comprised the following steps:
(1)White carbon is mixed with distilled water, is then stirred under ultrasound condition;
(2)Under agitation, inorganic base is added to into step(1)It is completely dissolved to inorganic base in the mixture for obtaining, then Process is dried to mixture;
(3)Step(2)Gained mixture carries out being porous silica after roasting, washing and dried.
2. method according to claim 1, it is characterised in that:Step(1)Described in white carbon and distilled water quality Than for 1:100~10:100.
3. method according to claim 2, it is characterised in that:Step(1)Described in white carbon and distilled water quality Than for 3:100~7:100.
4. method according to claim 1, it is characterised in that:Step(1)The middle stir process time is 1~10 h.
5. method according to claim 1, it is characterised in that:Step(2)Described in inorganic base be in NaOH, KOH, LiOH One or more.
6. method according to claim 1, it is characterised in that:Step(2)Described in white carbon and inorganic base mass ratio For 40:1~10:1.
7. method according to claim 6, it is characterised in that:Step(2)Described in white carbon and inorganic base mass ratio For 30:1~15:1.
8. method according to claim 1, it is characterised in that:Step(2)Described in dried temperature be less than 80 DEG C.
9. method according to claim 8, it is characterised in that:Step(2)Described in dried temperature be less than 70 DEG C.
10. method according to claim 1, it is characterised in that:Step(3)Described in sintering temperature be 300~900 DEG C, Roasting time is 1~15h.
11. methods according to claim 10, it is characterised in that:Step(3)Described in sintering temperature be 500~700 DEG C, Roasting time is 3~10h.
12. methods according to claim 1, it is characterised in that:Step(3)Described in drying be in 100~140 DEG C of conditions 5~15h of lower drying.
A kind of 13. porous silicas, it is characterised in that:The porous silica is will according to arbitrary right in claim 1-12 Method is asked to prepare.
CN201310503640.XA 2013-10-24 2013-10-24 Porous silica and preparation method thereof Active CN104556068B (en)

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CN106517218B (en) * 2015-09-14 2018-08-17 广州凌玮科技股份有限公司 A kind of method that template prepares large aperture silica-gel carrier

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1604914A (en) * 2001-12-20 2005-04-06 巴塞尔聚烯烃股份有限公司 Catalyst solid comprising pyrogenic silica for olefin polymerization
CN101767790A (en) * 2008-12-31 2010-07-07 中国石油化工股份有限公司 Dual-pore distribution silica synthesis method

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CN1049443C (en) * 1994-06-02 2000-02-16 中国科学院化学研究所 Preparing method for high porosity silicon dioxide particles
CN1157245C (en) * 2000-08-22 2004-07-14 中国石油化工股份有限公司 Macroporous silicon dioxide carrier and its preparing method
JP4860928B2 (en) * 2002-12-18 2012-01-25 エボニック デグサ ゲーエムベーハー Structurally modified silica

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1604914A (en) * 2001-12-20 2005-04-06 巴塞尔聚烯烃股份有限公司 Catalyst solid comprising pyrogenic silica for olefin polymerization
CN101767790A (en) * 2008-12-31 2010-07-07 中国石油化工股份有限公司 Dual-pore distribution silica synthesis method

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