CN102190306A - Silica microspheres and its preparation method - Google Patents
Silica microspheres and its preparation method Download PDFInfo
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Abstract
The invention relates to silica microspheres and its preparation method, which mainly solves the problem of the unavailable silica microspheres with a high specific surface area and pore volume existing in the prior art. Silica microspheres adopted in the invention is characterized in that the specific surface is 350 to 500 square meters per gram and the pore volume is 1.3 to 1.6 cubic centimeters per gram, and the invention also provides the method for producing the silica microspheres. The method comprises the following steps: (A) mixing water glass and a sulfuric acid aqueous solution for obtaining a mixed liquor with a pH value of 6.5 to 10; (B) dropping the mixed liquor obtained from the step (A) into an oil column forming device for producing hydrogel; (C) washing, aging, drying and roasting the hydrogel for obtaining silica, wherein an aqueous solution for aging contains at least one organosilicon from 2-(sodium sulfophenyl ) ethyl siloxane, 3-(sulfonate ) propyl group siloxane and 3-(sulfonate-2-hydroxy-propanolato) for solving the problem, the present invention can be used for the industrial production of silica microspheres.
Description
Technical field
The present invention relates to a kind of microsphere silica gel and preparation method thereof.
Background technology
Microsphere silica gel is a kind of porous material, is the support of the catalyst of using always.Specific surface and pore volume index according to microsphere silica gel can roughly roughly be divided into four classes to microsphere silica gel.The first kind, pore volume are generally 1.0～2.0 cubic centimetres/gram, and specific surface is generally 150～300 meters squared per gram, and this class silica gel is commonly referred to macroporous microsphere silica gel; Second class, pore volume are generally 0.8～1.2 cubic centimetre/gram, and specific surface is generally 300～500 meters squared per gram, and this class silica gel is commonly referred to the gross porosity microsphere silica gel; The 3rd class, pore volume are generally 0.60～0.65 cubic centimetre/gram, and specific surface is generally 450～650 meters squared per gram, and this class silica gel is commonly referred to the Type B microsphere silica gel; The 4th class, pore volume are generally 0.35～0.45 cubic centimetre/gram, and specific surface is generally 650～800 meters squared per gram, and this class silica gel is commonly referred to the pore microsphere silica gel.Microsphere silica gel as support of the catalyst, large specific surface helps the dispersion of catalyst activity component, thereby help improving activity of such catalysts and life-span, thereby and mass transfer and heat transfer that large pore volume often helps in the reaction process help improving selectivity of catalyst.The specific surface that improves microsphere silica gel tends to reduce pore volume, improve pore volume and can reduce specific surface again, this Changing Pattern in the specific surface of aforementioned microsphere silica gel and pore volume index also as can be seen.Chinese patent ZL96117058.1 discloses a kind of preparation method of silica gel of adjusting porous structure.This method adopts water glass to mix with sulfuric acid, adopt the method for forming oil column (the forming oil column devices that adopt U.S. Pat 2647875 to disclose) to make hydrogel, obtain silica gel product by operations such as washing, aging in water phase surfactant mixture, drying, roastings then.Technologies such as the proportioning between the different surfaces promoting agent, surfactant concentration have reached the purpose of regulating the silica gel pore structure in the surfactant soln by regulating in this invention.But the specific surface in its technical scheme is 80～500 meters squared per gram, and pore volume is 0.3～1.2 a cubic centimetre/gram, reaches at specific surface and can not reach the result of pore volume greater than 1.2 cubic centimetres/gram under the situation of 350～500 meters squared per gram.
Therefore, there is the technical problem to obtain all higher microsphere silica gel of specific surface and pore volume simultaneously in the prior art.
Chinese patent ZL20041009214.1 discloses a kind of engine coolant, and Chinese patent ZL200410009364.2 discloses a kind of method that improves engine coolant stability.In these two inventions 2-(sodium sulfophenyl) ethylsiloxane, 3-(sodium sulfonate) propyl-siloxane, 3-(sodium sulfonate-2-hydroxyl-propoxy-) propyl-siloxane are prevented silicate generation gelling in the engine coolant with used as stabilizers.
Summary of the invention
One of technical problem to be solved by this invention is the technical problem that prior art can't obtain all higher microsphere silica gel of specific surface area and pore volume, and a kind of new microsphere silica gel is provided.This silica gel has higher specific surface area, has high pore volume simultaneously.Two of technical problem to be solved by this invention provides preparation method a kind of and one of technical solution problem corresponding microsphere silica gel.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of microsphere silica gel, specific surface are 350～500 meters squared per gram, and pore volume is 1.3～1.6 a cubic centimetres/gram.Adopt the technical solution of the present invention to have obtained specific surface and all higher microsphere silica gel of pore volume, solved the technical problem that prior art can't obtain all higher microsphere silica gel of specific surface and pore volume.
For solve the problems of the technologies described above two, the technical scheme that the present invention takes is as follows: a kind of preparation method of microsphere silica gel comprises the steps: that (A) will be with SiO
2The meter weight concentration is 10～25% water glass with weight concentration is that 10～25% aqueous sulfuric acid mixes, and to make the pH of mixed solution be 6.5～10 by regulating these two kinds of material's proportion; (B) mixed solution that steps A is obtained splashes in the forming oil column device and to drip a ball forming and make hydrogel, and the hydrogel of generation is proposed by water layer; (C) hydrogel that step B is obtained comprises that washing, step aging, dry, roasting obtain silica gel, and wherein the aqueous solution of aging usefulness contains a kind of organosilicon in 2-(sodium sulfophenyl) ethylsiloxane, 3-(sodium sulfonate) propyl-siloxane, 3-(sodium sulfonate-2-hydroxyl-propoxy-) propyl-siloxane at least.
When hydrogel that step B obtains washing efficiency height among the step C when acid, along with increasing washing time, the pH of hydrogel needs to prolong, in order to improve detersive efficiency, o'clock also can be earlier soak 1-2 hour with the sulfuric acid of 1～4% (weight) pH 〉=8, and then carry out the washing among the step C.
Aging pH with the aqueous solution is 4～8 among the step C in technique scheme, and preferable range is 5～6.The digestion time preferable range is 5～48 hours, and the temperature preferable range is 40～95 ℃.Aging with organosilyl content in the aqueous solution by weight preferable range be 5～30%, more preferably scope is 10～25%, better preferable range is 15～20%.In order to improve aging effect, need to allow the organosilicon molecule to the inner fully diffusion of hydrogel before aging, therefore need be about to hydrogel earlier at room temperature fully soaks in containing the above-mentioned organosilyl aqueous solution, and soak time is generally and is no less than 3 hours, be preferably 4～8 hours, and then row is aging.
Drying temperature preferable range in the technique scheme among the step C is 80～150 ℃, and the maturing temperature preferable range is 400～600 ℃.
Adopt the preparation method of microsphere silica gel provided by the invention, the specific surface of the microsphere silica gel that obtains can reach 350～500 meters squared per gram, pore volume can reach 1.3～1.6 cubic centimetres/gram simultaneously, therefore have higher specific surface and pore volume simultaneously, solve the technical problem that prior art can't obtain all higher microsphere silica gel of specific surface and pore volume simultaneously, obtained better technical effect.
The key problem in technology of the inventive method, be with in engine refrigerating fluid for preventing that silicate stabilizers 2-(sodium sulfophenyl) ethylsiloxane, 3-(sodium sulfonate) propyl-siloxane, 3-(sodium sulfonate-2-hydroxyl-propoxy-) propyl-siloxane that silicate generation gelling is added are used for the weathering process of the preparation of oily moulding microsphere silica gel, the transition between the silicon hydroxyl is crosslinked to be had than high-ratio surface microsphere silica gel to have higher pore volume simultaneously thereby these silicate stabilizers may hinder in the weathering process of microballoon in the microsphere silica gel.
The invention will be further elaborated below by embodiment, and all embodiment and comparative example all adopt the disclosed shaped device of US2647875 to carry out " dripping ball forming " in oil column.
Embodiment
[embodiment 1]
(weight is with SiO with 15%
2Meter) sulfuric acid of water glass and 10% (weight) is mixed by the nozzle place, and to regulate pH of mixed to 6.5 be moulding in 50 ℃ the oil column in temperature then by regulating these two kinds of material proportions, and hydrogel takes out from oil column lower end water layer.Hydrogel with flowing water wash to elutant to 1% (weight) AgNO
3The aqueous solution reaction that is negative changes hydrogel over to isopyknic weight concentration then and is in 5% 2-(sodium sulfophenyl) the ethylsiloxane aqueous solution, is adjusted to pH8.0 with ammoniacal liquor, and soaking at room temperature 3 hours was warming up to 90 ℃ and insulation (promptly aging) 24 hours then.Filter, with the hydrogel after aging in 80 ℃ of air dry ovens dry 8 hours, roasting 4 hours in 400 ℃ muffle furnace then.Recording the microsphere silica gel specific surface area is 357 meters squared per gram, and pore volume is 1.3 a cubic centimetres/gram.
For ease of relatively the character of part processing condition and microsphere silica gel being listed in the table 1.
[comparative example 1]
Be the comparative example of [embodiment 1], carry out with reference to the embodiment among the Chinese patent ZL96117058.1 2.
(weight is with SiO with 15%
2Meter) sulfuric acid of water glass and 10% (weight) is mixed by the nozzle place, and to regulate pH of mixed to 6.5 be moulding in 50 ℃ the oil column in temperature then by regulating these two kinds of material proportions, and hydrogel takes out from oil column lower end water layer.Hydrogel with flowing water wash to elutant to 1% (weight) AgNO
3The aqueous solution reaction that is negative changes hydrogel over to isopyknic weight concentration then and is in 0.2% the aliphatic alcohol polyethenoxy aqueous sodium persulfate solution, is adjusted to pH8.0 with ammoniacal liquor, and soaking at room temperature 3 hours was warming up to 90 ℃ and insulation (promptly aging) 24 hours then.Filter, with the hydrogel after aging in 80 ℃ of air dry ovens dry 8 hours, roasting 4 hours in 400 ℃ muffle furnace then.Recording the microsphere silica gel specific surface area is 327 meters squared per gram, and pore volume is 1.1 a cubic centimetres/gram.Specific surface and pore volume are all less than the result of the present invention [embodiment 1].
For ease of relatively the character of part processing condition and microsphere silica gel being listed in the table 1.
[embodiment 2]
(weight is with SiO with 10%
2The sulfuric acid of water glass and 15% (weight) meter) is mixed by the nozzle place, regulates pH of mixed to 7.0 by regulating this two kinds of material proportions, is moulding in 80 ℃ the oil column in temperature then, and hydrogel proposes from oil column lower end water layer.Hydrogel is washed with water to elutant to 1% (weight) AgNO
3The aqueous solution reaction that is negative changes hydrogel over to isopyknic weight concentration then and is in 30% 3-(sodium sulfonate) the propyl-siloxane aqueous solution, is adjusted to pH6.0 and soaking at room temperature 4 hours with acetic acid, be warming up to then 40 ℃ aging 48 hours.Filter, with the hydrogel after aging in 120 ℃ of air dry ovens dry 8 hours, roasting 4 hours in 600 ℃ muffle furnace then.Recording the microsphere silica gel specific surface area is 372 meters squared per gram, and pore volume is 1.5 a cubic centimetres/gram.
For ease of relatively the main technique condition being listed in the table 1.
[embodiment 3]
(weight is with SiO with 15%
2The sulfuric acid of water glass and 20% (weight) meter) is mixed by the nozzle place, regulates pH of mixed to 8.0 by regulating this two kinds of material proportions, is moulding in 65 ℃ the oil column in temperature then, and hydrogel proposes from oil column lower end water layer.Hydrogel is washed with water to elutant to 1% (weight) AgNO
3The aqueous solution reaction that is negative, then hydrogel is changed over to isopyknic weight concentration and be in 17% 3-(sodium sulfonate-2-hydroxyl-propoxy-) the propyl-siloxane aqueous solution, be adjusted to pH6.0 and soaking at room temperature 5 hours with acetic acid, be warming up to then 60 ℃ aging 12 hours.Filter, with the hydrogel after aging in 90 ℃ of air dry ovens dry 8 hours, roasting 4 hours in 450 ℃ muffle furnace then.Recording the microsphere silica gel specific surface area is 476 meters squared per gram, and pore volume is 1.5 a cubic centimetres/gram.
For ease of relatively the main technique condition being listed in the table 1.
[embodiment 4]
(weight is with SiO with 20%
2The sulfuric acid of water glass and 25% (weight) meter) is mixed by the nozzle place, regulates pH of mixed to 7.5 by regulating this two kinds of material proportions, is moulding in 90 ℃ the oil column in temperature then, and hydrogel proposes from oil column lower end water layer.Hydrogel is washed with water to elutant to 1% (weight) AgNO
3The aqueous solution reaction that is negative changes hydrogel over to isopyknic weight concentration then and is in 18% 3-(sodium sulfonate) the propyl-siloxane aqueous solution, is adjusted to pH5.5 and soaking at room temperature 4 hours with acetic acid, be warming up to then 85 ℃ aging 8 hours.Filter, with the hydrogel after aging in 140 ℃ of air dry ovens dry 8 hours, roasting 4 hours in 500 ℃ muffle furnace then.Recording the microsphere silica gel specific surface area is 491 meters squared per gram, and pore volume is 1.6 a cubic centimetres/gram.
For ease of relatively the main technique condition being listed in the table 1.
[embodiment 5]
(weight is with SiO with 20%
2The sulfuric acid of water glass and 25% (weight) meter) is mixed by the nozzle place, regulate pH of mixed to 9.0 by regulating these two kinds of material proportions, be moulding in 75 ℃ the oil column in temperature then, hydrogel proposes from oil column lower end water layer, be 2% aqueous sulfuric acid immersion hydrogel 2 hours earlier, be washed with water to elutant then 1% (weight) AgNO with weight concentration
3The aqueous solution reaction that is negative changes hydrogel over to isopyknic weight concentration then and is in 19% 3-(sodium sulfonate-2-hydroxyl-propoxy-) the propyl-siloxane aqueous solution, is adjusted to pH5.5 and soaking at room temperature 6 hours with acetic acid, be warming up to then 85 ℃ aging 6 hours.Filter, with the hydrogel after aging in 130 ℃ of air dry ovens dry 8 hours, roasting 4 hours in 500 ℃ muffle furnace then.Recording the microsphere silica gel specific surface area is 486 meters squared per gram, and pore volume is 1.6 a cubic centimetres/gram.
For ease of relatively the main technique condition being listed in the table 1.
[embodiment 6]
(weight is with SiO with 10%
2The sulfuric acid of water glass and 10% (weight) meter) is mixed by the nozzle place, regulate pH of mixed to 8.0 by regulating these two kinds of material proportions, be moulding in 85 ℃ the oil column in temperature then, hydrogel proposes from oil column lower end water layer, is washed with water to elutant to 1% (weight) AgNO
3The aqueous solution reaction that is negative, then hydrogel being changed over to isopyknic weight concentration is in the aqueous solution of 16% organosilicon (3-(sodium sulfonate) propyl-siloxane that contains 2-(sodium sulfophenyl) ethylsiloxane and 6% (weight) of 10% (weight)), be adjusted to pH5.0 and soaking at room temperature 5 hours with acetic acid, be warming up to then 80 ℃ aging 10 hours.Filter, with the hydrogel after aging in 120 ℃ of air dry ovens dry 8 hours, roasting 4 hours in 550 ℃ muffle furnace then.Recording the microsphere silica gel specific surface area is 447 meters squared per gram, and pore volume is 1.5 a cubic centimetres/gram.
For ease of relatively the main technique condition being listed in the table 1.
[embodiment 7]
(weight is with SiO with 10%
2The sulfuric acid of water glass and 15% (weight) meter) is mixed by the nozzle place, regulate pH of mixed to 9.5 by regulating these two kinds of material proportions, be moulding in 70 ℃ the oil column in temperature then, hydrogel proposes from oil column lower end water layer, is washed with water to elutant to 1% (weight) AgNO
3The aqueous solution reaction that is negative changes hydrogel over to isopyknic weight concentration then and is in 15% 3-(sodium sulfonate-2-hydroxyl-propoxy-) the propyl-siloxane aqueous solution, is adjusted to pH4.0 and soaking at room temperature 3 hours with acetic acid, be warming up to then 90 ℃ aging 6 hours.Filter, with the hydrogel after aging in 100 ℃ of air dry ovens dry 8 hours, roasting 4 hours in 600 ℃ muffle furnace then.Recording the microsphere silica gel specific surface area is 419 meters squared per gram, and pore volume is 1.5 a cubic centimetres/gram.
For ease of relatively the main technique condition being listed in the table 1.
[embodiment 8]
(weight is with SiO with 25%
2The sulfuric acid of water glass and 20% (weight) meter) is mixed by the nozzle place, regulate pH of mixed to 10.0 by regulating these two kinds of material proportions, be moulding in 95 ℃ the oil column in temperature then, hydrogel proposes from oil column lower end water layer, be 3% aqueous sulfuric acid immersion hydrogel 2 hours earlier, be washed with water to elutant then 1% (weight) AgNO with weight concentration
3The aqueous solution reaction that is negative, changing hydrogel over to isopyknic weight concentration is in 10% 2-(sodium sulfophenyl) the ethylsiloxane aqueous solution, is adjusted to pH5.0 and soaking at room temperature 3 hours with acetic acid, be warming up to then 95 ℃ aging 5 hours.Filter, with the hydrogel after aging in 150 ℃ of air dry ovens dry 8 hours, roasting 4 hours in 550 ℃ muffle furnace then.Recording the microsphere silica gel specific surface area is 362 meters squared per gram, and pore volume is 1.4 a cubic centimetres/gram.For ease of relatively the main technique condition being listed in the table 1.
Claims (10)
1. microsphere silica gel, the specific surface area that it is characterized in that microsphere silica gel is 350～500 meters squared per gram, pore volume is 1.3～1.6 a cubic centimetres/gram.
2. the preparation method of the described microsphere silica gel of claim 1 comprises the steps:
(A) will be with SiO
2The meter weight concentration is 10～25% water glass with weight concentration is that 10～25% aqueous sulfuric acid mixes, and is 6.5～10 by regulating the pH that two kinds of material's proportion make mixed solution;
(B) mixed solution that steps A is obtained splashes in the forming oil column device and to drip a ball forming and make hydrogel, and the hydrogel of generation is proposed by water layer;
(C) hydrogel that step B is obtained comprises that washing, aging, dry, roasting obtain silica gel, and wherein the aqueous solution of aging usefulness contains a kind of organosilicon in 2-(sodium sulfophenyl) ethylsiloxane, 3-(sodium sulfonate) propyl-siloxane, 3-(sodium sulfonate-2-hydroxyl-propoxy-) propyl-siloxane at least.
3. the preparation method of microsphere silica gel according to claim 2 is characterized in that aging pH with the aqueous solution is 4～8.
4. the preparation method of microsphere silica gel according to claim 3 is characterized in that aging pH with the aqueous solution is 5～6.
5. the preparation method of microsphere silica gel according to claim 2 is characterized in that digestion time is 5～48 hours, and temperature is 40～95 ℃.
6. the preparation method of microsphere silica gel according to claim 2 is characterized in that aging is 5～30% with organosilyl weight content in the aqueous solution.
7. the preparation method of microsphere silica gel according to claim 6 is characterized in that aging is 10～25% with organosilyl weight content in the aqueous solution.
8. the preparation method of microsphere silica gel according to claim 7 is characterized in that aging is 15～20% with organosilyl weight content in the aqueous solution.
9. the preparation method of microsphere silica gel according to claim 2 is characterized in that drying temperature is 80～150 ℃.
10. the preparation method of microsphere silica gel according to claim 2 is characterized in that maturing temperature is 400～600 ℃.
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Cited By (2)
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| CN102794202A (en) * | 2012-08-17 | 2012-11-28 | 垦利三合新材料科技有限责任公司 | Preparation method of aperture controllable catalyst carrier silicone |
| CN104449319A (en) * | 2014-12-10 | 2015-03-25 | 三棵树涂料股份有限公司 | Specific water-based paint for indicating whiteness of wall surface through humidity sensitivity and preparation method thereof |
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| JP7055816B2 (en) * | 2016-12-04 | 2022-04-18 | イーエックスオー イメージング インコーポレイテッド | Low voltage, low power MEMS transducer with direct interconnection function |
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| CN102794202A (en) * | 2012-08-17 | 2012-11-28 | 垦利三合新材料科技有限责任公司 | Preparation method of aperture controllable catalyst carrier silicone |
| CN104449319A (en) * | 2014-12-10 | 2015-03-25 | 三棵树涂料股份有限公司 | Specific water-based paint for indicating whiteness of wall surface through humidity sensitivity and preparation method thereof |
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| CN102190306B (en) | 2012-11-14 |
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