CN104556067A - Porous silica and synthesis method thereof - Google Patents
Porous silica and synthesis method thereof Download PDFInfo
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- CN104556067A CN104556067A CN201310503639.7A CN201310503639A CN104556067A CN 104556067 A CN104556067 A CN 104556067A CN 201310503639 A CN201310503639 A CN 201310503639A CN 104556067 A CN104556067 A CN 104556067A
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Abstract
The invention provides porous silica and a synthesis method thereof. The method provided by the invention comprises the synthesis steps: (1) mixing silica sol and distilled water, and then, uniformly stirring; (2) adding an inorganic base into the mixture obtained in the step (1) under the condition of stirring, adjusting the pH value of a system to 10-14, and then, drying the mixture; (3) roasting the mixture obtained in the step (2), washing and drying, thereby obtaining the porous silica. The porous silica prepared by the method has the particle size of 3-8 microns, has the characteristic of mesoporous distribution and has the pore size variation range of 5-400nm. 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
Technical field
The invention belongs to porous inorganic material synthesis field, specifically a kind of porous silica silicon materials and synthetic method thereof.
Background technology
Porous oxidation silicon materials have broad application prospects in fields such as catalysis, absorption, separation, biomaterial, energy and environment.Technology prepared by current porous oxidation silicon materials is very ripe, but also in development, such as mesoporous silicon oxide, being also referred to as meso-porous molecular sieve material is exactly a study hotspot, and the kind prepared is also many, as M41S series, SBA15 etc.The synthesis of mesopore molecular sieve needs tensio-active agent, and several materials such as water, silicon source, acid or alkali, wherein tensio-active agent is the factor of most critical as template.More deep due to what study, it is also proposed many theories, such as liquid crystal templated mechanism, bar-shaped self-assembly model, charge matching mechanism, stratiform wrinkle model etc.
In addition also have macropore silicon oxide, the synthesis preparation of multistage pore canal silica material also gets most of the attention, and many materials are applied in many fields of industry.CN102070152 A functionalization equal grain porous silica microballoon and its preparation method and application, discloses a kind of porous silica silicon preparation method.The previously prepared equal grain porous polymer microsphere of this patent, as methacrylic acid fat, single polymers of Styrene and its derivatives or copolymer microsphere etc., and carries out surface-functionalized process to porous polymer microsphere, obtains the equal grain porous polymer microsphere of functionalization; (2) the dispersion of functionalization porous polymer microsphere in aqueous, then add silica precursor preparation and form complex microsphere in the middle of silicon-dioxide/polymkeric substance; (3) complex microsphere in the middle of silicon-dioxide/polymkeric substance is added heat extraction polymkeric substance, obtain equal grain porous silica microballoon; (4) use chemical reagent to carry out finishing to equal grain porous silica microballoon and form functional group.But the method is due to the organic template of the costliness of use, and as single polymers or the copolymer microsphere of Styrene and its derivatives, and operation steps is complicated, and preparation cost is too high.
" modern geology " (20 volumes the 4th phase in 2006) discloses a kind of preparation method of porous silica " to utilize coal ash for manufacturing for the experiment of porous silica ".The method utilizes phase separation principle, and take flyash as the silicic acid gel that raw material obtains after sial is separated, select polyvinyl alcohol to be pore-forming material, nitric acid is catalyzer, prepares a kind of porous silica containing three grades of ducts.The primary particle of this material is the microballoon of about 3 μm, macropore about 1 ~ 2 μm.But the specific surface area of the silicon oxide that the method obtains is too little, only has 12.03 m
2/ g, Application Areas is narrower.
" xylogen trimethyl quaternary ammonium salt is that template prepares porous oxidation silicon materials " " Beijing Forestry University's journal " (33 volumes the 4th phase in 2011) discloses a kind of preparation method of porous silica.Article with xylogen trimethyl quaternary ammonium salt be template, tetraethoxy for silicon source, adopt sol-gel method and roasting demoulding legal system for porous oxidation silicon materials.The aperture of this material is mainly distributed in 2.7 ~ 5.6 nm, and mean pore size is 21.4 nm.But the method employs the poisonous organic reagent such as a large amount of Trimethylamine 99, epoxy chloropropane when preparing template xylogen trimethyl quaternary ammonium salt, and preparation cost is high, and severe operational environment.
CN1339329A macroporous silicon dioxide carrier and preparation method thereof, discloses a kind of macroporous silicon dioxide carrier and preparation method thereof.This patent is first by alkali-metal inorganic salt deionized water dissolving, is mixed with double salt dipping solution; Again by the dipping solution impregnate porous matrix that the 1st step obtains, then dry, roasting obtains macroporous silicon dioxide carrier finished product.The mean pore size of this material is 30-600 nm, but after aperture is more than 50nm, its specific surface area sharply reduces, and specific surface area is too low.
The preparation method of CN1113923A high porosity silicon dioxide particles, discloses a kind of porous silica silicon preparation method.This patent is with common silica gel for raw material, adopts soda acid to corrode silica gel under certain temperature condition, such as 25 degree of process 6 hours in hydrofluoric acid.The method is similar to the process that the aftertreatment of zeolite soda acid manufactures secondary pore, owing to being the pore-creating of acid and alkali corrosion silica gel, must cause 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, adopts expensive organism as template or organic additive mostly, and operation steps also comparison step, these all cause the preparation cost of material too high, hinder this type of technology and move towards industrial production from laboratory.And prior art to need in exotic materials to improve preparing, such as in the control of size and pattern, the control method of pore size distribution and pore size also has huge room for promotion.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of porous silica and synthetic method thereof.Porous silica provided by the invention has excellent porous character, and preparation method is simple, and production cost is low.
Porous silica provided by the invention has following feature: consist of soft silica, and granular size is 3 ~ 8 μm, and particle is made up of the silica primary particles of 20 ~ 60nm, and specific surface area is 50 ~ 200m
2/ g, has grade pore distribution feature, and aperture is 5 ~ 400nm.
The synthetic method of porous silica of the present invention, comprises the following steps:
(1) silicon sol is mixed with distilled water, then stir;
(2) under agitation, mineral alkali is joined step (1) and obtain in mixture, the pH value regulating mixture is 10 ~ 14, then carries out drying treatment to mixture;
(3) porous silica is after step (2) gained mixture carries out roasting, washing and drying treatment.
According to synthetic method of the present invention, in the mixture described in step (1), the content of silicon-dioxide is 5 ~ 30wt%, preferably 10 ~ 20wt%.Wherein the silicon sol described in step (1) is general industry commodity, and preferred dioxide-containing silica is the silicon sol of 25wt% ~ 30wt%.
The stir process time described in step (1) is 1 ~ 3 h.
Mineral alkali described in step (2) can be one or more in NaOH, KOH, LiOH, preferred NaOH.
Described in step (2), drying treatment temperature is less than 80 DEG C, is preferably less than 70 DEG C.
Described in step (3), maturing temperature is 300 ~ 900 DEG C, preferably 500 ~ 700 DEG C; Roasting time is 1 ~ 15h, preferably 3 ~ 10h; Described washing is with deionized water wash to neutral, and described drying is dry 5 ~ 15h under 100 ~ 140 DEG C of conditions.
Porous silica provided by the invention is the porous silica with certain pattern, can be used as support of the catalyst, sorbent material, chromatographic column filler, also can be used as the synthesis masterplate of inorganic organic materials.
Compared with prior art, porous silica provided by the invention and preparation method thereof has the following advantages:
(1) the invention provides porous silica and have unique physicochemical characteristic, its particle size can control at 3 ~ 8 μm, and even particle size distribution; Pore size distribution has mesoporous distribution characteristics, and the variation range in aperture is 5 ~ 400 nm, and substance diffusion can be excellent.
(2) porous silica of the present invention and preparation method thereof is simple, and topmost feature does not use expensive poisonous organic formwork agent or additive, also not with the organosilicon of costliness for silicon source, so manufacturing cost is low.
(3), in the inventive method, the silicon sol as raw material then exists with silica gel liquid solution, and its colloidal particle is very small.Through the process of the inventive method, alkali is adsorbed on outside surface by the silicon oxide particle in silicon sol, after heat treatment there is chemical action, stronger chemical bond is formed between molecule, therefore formed and there is equally distributed grade duct, and by the size controlling of offspring at 3 ~ 8 μm, become the poriness silicon oxide material of the certain function of tool.
Accompanying drawing explanation
The low power SEM photo of the porous silica that Fig. 1 embodiment 1 is synthesized.
The high power SEM photo of the porous silica that Fig. 2 embodiment 1 is synthesized.
Embodiment
Below by specific embodiment, detailed description is given to porous oxidation silicon preparation method of the present invention, but be not limited to embodiment.
Embodiment 1
(1) be that 30% silicon sol mixes with 50 mL distilled water by 50 mL concentration, stir 2 h.
(2) sodium hydroxide being joined step (1) obtains in mixture, and regulation system pH value is 13; Stir 10 min; Then dry by moisture evaporate to dryness under the condition of 60 DEG C.
(3) step (2) is obtained mixture roasting 5 h under 600 DEG C of conditions; Be washed with distilled water to neutrality again, at 120 DEG C of drying 12 h, obtain porous silica, be numbered CL1.
Embodiment 2
(1) be that 30% silicon sol mixes with 40 mL distilled water by 50 mL concentration, stir 2 h.
(2) sodium hydroxide being joined step (1) obtains in mixture, and adjust ph is 12; Stir 10 min; Then dry by moisture evaporate to dryness under lower than the condition of 50 DEG C.
(3) step (2) is obtained mixture roasting 5 h under 650 DEG C of conditions; Be washed with distilled water to neutrality again, at 120 DEG C of drying 12 h, obtain porous silica, be numbered CL2.
Embodiment 3
(1) be that 30% silicon sol mixes with 50 mL distilled water by 40 mL concentration, stir 2 h.
(2) sodium hydroxide being joined step (1) obtains in mixture, and condition pH value is 13; Stir 10 min; Then dry by moisture evaporate to dryness under lower than the condition of 60 DEG C.
(3) step (2) is obtained mixture roasting 5 h under 600 DEG C of conditions; Be washed with distilled water to neutrality again, at 120 DEG C of drying 12 h, obtain porous silica, be numbered CL3.
Embodiment 4
(1) be that 30% silicon sol mixes with 50 mL distilled water by 50 mL concentration, stir 2 h.
(2) sodium hydroxide being joined step (1) obtains in mixture, and adjust ph is 13; Then dry by moisture evaporate to dryness under lower than the condition of 35 DEG C.
(3) step (2) is obtained mixture roasting 7 h under 550 DEG C of conditions; Be washed with distilled water to neutrality again, at 120 DEG C of drying 12 h, obtain porous silica, be numbered CL4.
Embodiment 5
(1) be that 30% silicon sol mixes with 50 mL distilled water by 30 mL concentration, stir 2 h.
(2) sodium hydroxide being joined step (1) obtains in mixture, and adjust ph is 13; Then dry by moisture evaporate to dryness under the condition of 55 DEG C.
(3) step (2) is obtained mixture roasting 8 h under 500 DEG C of conditions; Be washed with distilled water to neutrality again, at 120 DEG C of drying 12 h, obtain porous silica, be numbered CL5.
Table 1 is embodiment gained sample physico-chemical property
Claims (12)
1. a porous silica, has following feature: consist of soft silica, and granular size is 3 ~ 8 μm, and particle is made up of the silica primary particles of 20 ~ 60nm, and specific surface area is 50 ~ 200m
2/ g, has grade hole characteristic, and aperture is 5 ~ 400nm.
2. the preparation method of porous silica described in claim 1, comprises the following steps:
(1) silicon sol is mixed with distilled water, then stir;
(2) under agitation, mineral alkali is joined step (1) and obtain in mixture, regulation system pH value is 10 ~ 14, then carries out drying treatment to mixture;
(3) porous silica is after step (2) gained mixture carries out roasting, washing and drying treatment.
3. method according to claim 2, is characterized in that: in step (1), the stir process time is 1 ~ 10 h.
4. method according to claim 2, is characterized in that: in the mixture described in step (1), the content of silicon-dioxide is 5wt% ~ 30wt%.
5. the method according to claim 2 or 4, is characterized in that: in the mixture described in step (1), the content of silicon-dioxide is 10wt% ~ 20wt%.
6. method according to claim 2, is characterized in that: in described silicon sol, dioxide-containing silica is 25wt% ~ 30wt%.
7. method according to claim 2, is characterized in that: mineral alkali described in step (2) is one or more in NaOH, KOH, LiOH.
8. method according to claim 2, is characterized in that: described in step (2), drying treatment temperature is less than 80 DEG C.
9. method according to claim 8, is characterized in that: described in step (2), drying treatment temperature is less than 70 DEG C.
10. method according to claim 2, is characterized in that: described in step (3), maturing temperature is 300 ~ 900 DEG C, and roasting time is 1 ~ 15h.
11. methods according to claim 2 or 10, it is characterized in that: described in step (3), maturing temperature is 500 ~ 700 DEG C, roasting time is 3 ~ 10h.
12. methods according to claim 2, is characterized in that: described drying is 5 ~ 15h dry under 100 ~ 140 DEG C of conditions.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111717922A (en) * | 2020-07-01 | 2020-09-29 | 石河子大学 | Preparation method of spherical silicon dioxide |
| CN114804128A (en) * | 2022-04-18 | 2022-07-29 | 安徽壹石通材料科技股份有限公司 | Spherical silicon dioxide treatment method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113923A (en) * | 1994-06-02 | 1995-12-27 | 中国科学院化学研究所 | Preparing method for high porosity silicon dioxide particles |
| CN1339329A (en) * | 2000-08-22 | 2002-03-13 | 中国石油化工股份有限公司 | Macroporous silicon dioxide carrier and its preparing method |
| US20040127604A1 (en) * | 2002-12-18 | 2004-07-01 | Degussa Ag | Structurally coated silica |
| 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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- 2013-10-24 CN CN201310503639.7A patent/CN104556067B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113923A (en) * | 1994-06-02 | 1995-12-27 | 中国科学院化学研究所 | Preparing method for high porosity silicon dioxide particles |
| CN1339329A (en) * | 2000-08-22 | 2002-03-13 | 中国石油化工股份有限公司 | Macroporous silicon dioxide carrier and its preparing method |
| 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 |
| US20040127604A1 (en) * | 2002-12-18 | 2004-07-01 | Degussa Ag | Structurally coated silica |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111717922A (en) * | 2020-07-01 | 2020-09-29 | 石河子大学 | Preparation method of spherical silicon dioxide |
| CN114804128A (en) * | 2022-04-18 | 2022-07-29 | 安徽壹石通材料科技股份有限公司 | Spherical silicon dioxide treatment method |
| CN114804128B (en) * | 2022-04-18 | 2023-08-29 | 蚌埠壹石通电子通信材料有限公司 | Spherical silicon dioxide treatment method |
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