CN104556068A - Porous silica and preparation method thereof - Google Patents
Porous silica and preparation method thereof Download PDFInfo
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- CN104556068A CN104556068A CN201310503640.XA CN201310503640A CN104556068A CN 104556068 A CN104556068 A CN 104556068A CN 201310503640 A CN201310503640 A CN 201310503640A CN 104556068 A CN104556068 A CN 104556068A
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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
Technical field
The invention belongs to porous inorganic material synthesis field, specifically a kind of porous silica silicon materials and preparation 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 ~ 600nm, 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 the deficiency that prior art exists, the invention provides a kind of porous silica and preparation method thereof.
Porous silica provided by the invention has excellent porous character, and preparation method is simple, and production cost is low.
The invention provides a kind of porous silica, have following feature: consist of soft silica, granular size is 10 ~ 20 μm, and particle is made up of the silica primary particles of 30 ~ 60nm, and specific surface area is 50 ~ 150 m
2/ g, has grade pore distribution feature, and aperture is 10 ~ 50nm.
The preparation method of porous silica of the present invention, comprises the following steps:
(1) white carbon black is mixed with distilled water, then under ultrasound condition, carry out stir process;
(2) under agitation, mineral alkali is joined in the mixture that step (1) obtains and dissolve completely to mineral alkali, then drying treatment is carried out 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, wherein the white carbon black described in step (1) is general industry commodity, and preferred size is less than the white carbon black of 60nm.
The mass ratio of the white carbon black described in step (1) and distilled water is 1:100 ~ 10:100, preferred 3:100 ~ 7:100.
In step (1), the stir process time is 1 ~ 10 h, preferably 3 ~ 7 h.
Mineral alkali described in step (2) can be one or more in NaOH, KOH, LiOH, preferred NaOH.
Described in step (2), the mass ratio of white carbon black and mineral alkali is 40:1 ~ 10:1, preferred 30:1 ~ 15:1.
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 10 ~ 20 μm, 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 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 white carbon black molecule as raw material exists with dispersion state, is deposited in together, can not forms the offspring with definite shape and size between particle by the loose absorption of Van der Waals force, more can not the duct of formation rule.After the inventive method process, alkali is adsorbed on outside surface by silica particles, after heat treatment there is chemical action, reactive force between molecule becomes stronger chemical bond from faint Van der Waals force, formation has foramen magnum-mesoporous equally distributed grade duct, and the particle diameter of offspring is within the scope of 10 ~ 20 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) 5 g white carbon blacks are mixed with 100 mL distilled water, stir process 5 h under ultrasound condition.
(2) 0.25 g sodium hydroxide being joined step (1) obtains in mixture, stirs 3 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) 4 g white carbon blacks are mixed with 100 mL distilled water, under ultrasound condition, stir 5.5 h.
(2) 0.15 g sodium hydroxide being joined step (1) obtains in mixture, stirs 3 min; Then dry by moisture evaporate to dryness under 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) 6 g white carbon blacks are mixed with 80 mL distilled water, under ultrasound condition, stir 5 h.
(2) 0.3 g sodium hydroxide being joined step (1) obtains in mixture, stirs 3 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 CL3.
Embodiment 4
(1) 7 g white carbon blacks are mixed with 100 mL distilled water, under ultrasound condition, stir 5 h.
(2) 0.5 g sodium hydroxide being joined step (1) obtains in mixture, stirs 3 min; Then dry by moisture evaporate to dryness under 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) 5.5g white carbon black is mixed with 70 mL distilled water, under ultrasound condition, stir 5 h.
(2) 0.55g sodium hydroxide being joined step (1) obtains in mixture, stirs 3 min; 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 10 ~ 20 μm, and particle is made up of the silica primary particles of 30 ~ 60nm, and specific surface area is 50 ~ 150 m
2/ g, has grade pore distribution feature, and aperture is 10 ~ 500 nm.
2. the preparation method of porous silica described in claim 1, comprises the following steps:
(1) white carbon black is mixed with distilled water, then under ultrasound condition, carry out stir process;
(2) under agitation, mineral alkali is joined in the mixture that step (1) obtains and dissolve completely to mineral alkali, then drying treatment is carried out 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: the mass ratio of the white carbon black described in step (1) and distilled water is 1:100 ~ 10:100.
4. according to the method in claim 2 or 3, it is characterized in that: the mass ratio of the white carbon black described in step (1) and distilled water is 3:100 ~ 7:100.
5. method according to claim 2, is characterized in that: in step (1), the stir process time is 1 ~ 10 h.
6. method according to claim 2, is characterized in that: mineral alkali described in step (2) is one or more in NaOH, KOH, LiOH.
7. method according to claim 2, is characterized in that: described in step (2), the mass ratio of white carbon black and mineral alkali is 40:1 ~ 10:1.
8. the method according to claim 2 or 7, is characterized in that: described in step (2), the mass ratio of white carbon black and mineral alkali is 30:1 ~ 15:1.
9. method according to claim 2, is characterized in that: described in step (2), drying treatment temperature is less than 80 DEG C, is preferably 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, is characterized in that: described in step (3), maturing temperature is 500 ~ 700 DEG C, and 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517218A (en) * | 2015-09-14 | 2017-03-22 | 广州凌玮科技股份有限公司 | Method for preparing silica gel carrier of large aperture by template 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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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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517218A (en) * | 2015-09-14 | 2017-03-22 | 广州凌玮科技股份有限公司 | Method for preparing silica gel carrier of large aperture by template method |
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