CN106698444A - Hypergravity liquid precipitation method of preparing silicone dioxide nanometer granule based on rice hull ash - Google Patents
Hypergravity liquid precipitation method of preparing silicone dioxide nanometer granule based on rice hull ash Download PDFInfo
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- CN106698444A CN106698444A CN201611006946.4A CN201611006946A CN106698444A CN 106698444 A CN106698444 A CN 106698444A CN 201611006946 A CN201611006946 A CN 201611006946A CN 106698444 A CN106698444 A CN 106698444A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention relates to a production method of extracting the silicone dioxide nanometer granules using the hypergravity liquid precipitation method based on the rice hull ash. The method comprises the steps that rice hull ash is used as the raw material, a hypergravity container is adopted to replace an acidification stirring reaction kettle, and surfactant is added in the reaction liquid; the costs are greatly reduced, the time for acidification reaction is shortened, and efficiency and product quality are increased. The obtained silicone dioxide is high in purity, small in granule diameter and even in distribution; the silicone dioxide can be widely applied in the fields of catalysts, additives and the like, and has a good prospect.
Description
Technical field
The present invention relates to a kind of hypergravity liquid liquid precipitate method for preparing nano SiO 2 particle based on rice hull ash, belong to
Chemical technology field.
Background technology
China is the most abundant country of rice husk resource in the world, accounts for the 37% of world's paddy total output, is occupied first place in the world.It is existing
In the stage, combustion heat supplying or generating are generally used in the rice husk produced by China, to rice husk by the use of in the past be partial to always as
The energy, but still can remaining substantial amounts of rice hull ash after having utilized.Element silicon and carbon are rich in rice hull ash, are generally regarded
Abandoned for agricultural wastes, not only polluted environment, also result in the wasting of resources.As people are to environment and biology
Matter resource is re-recognized, and the utilization to rice hull ash has gradually been taken seriously.Currently known rice hull ash purposes includes preparing
Molecular sieve, activated carbon, catalyst carrier, silica of high-quality etc..
Prepare nanometer grade silica production method and be basically divided into vapor phase method and liquid phase method.Vapor phase method is mainly silicon halide
Pyrohydrolysis is carried out in the water of oxyhydrogen flame generation to be obtained.The advantage of vapor phase method is product purity high and spherical in shape, dispersiveness
Can be good, surface hydroxyl is few, and particle is thin, thus with good reinforcing property, but expensive starting materials, high energy consumption, technical sophistication, equipment
It is required that high, these shortcomings limit the application of product.
Other liquid phase method is mainly acid precipitation method, by being acidified silicate, obtains the silica dioxide granule of scattered porosity.Mesh
Preceding main acid precipitation method is sulfuric acid acidization, prepares that silica, production technology, technique, equipment is simple, raw material with acid precipitation method
Wide material sources, low production cost, but product cut size are big, activity is relatively low, particle is whard to control, affinity is poor, product quality phase
To relatively low.
The content of the invention
The purpose of the present invention is intended to optimize the deficiencies in the prior art, there is provided one kind utilizes rice hull ash, while acid can be shortened
The method that the change reaction time prepares high-quality nano silicon.The present invention with rice hull ash as raw material, using overweight force container generation
For acidifying stirred autoclave, and surfactant, cost is added to substantially reduce in the reaction, when can not only shorten acidification reaction
Between, improve efficiency and can also improve product quality.
The present invention is achieved by the following technical solutions：
A kind of preparation method of nano SiO 2 particle, comprises the following steps：
(1) to acid solution is added in rice hull ash, rice hull ash is immersed in described acid solution, be heated to reflux 1~5 small
When, dry solid product is washed to neutrality with water, the substance withdrawl syndrome of the acid is 0.1~5mol/L；
(2) to alkaline solution is added in step (1) gained solid product, it is heated to reflux 1~5 hour, after reaction terminates, takes out
Filter, and use hot wash filter residue, the filtrate for obtaining as water glass solution, be incubated it is standby, the alkaline solution concentration for 0.1~
10mol/L；
(3) surfactant is added in the water glass solution of step (2) acquisition and obtains mixed liquor, then by mixed liquor
It is 1 with the flow-rate ratio of liquid-phase precipitation agent:Mixed liquor after preheating and liquid-phase precipitation agent are passed through hypergravity rotation by 1~20 simultaneously
Bed, obtains slurries, and pH adjusting agent is made with ammoniacal liquor, adjusts pH to 8-10, insulation 0.25~2h of ageing, and pH adjusting agent is made with sulfuric acid, adjusts
Section pH to 1-3, then filters, and gained filter cake is washed with water to neutrality, and heat drying, powder obtained by after crushing is silica
Nano particle；The liquid-phase precipitation agent is the mixed acid of sulfuric acid solution, hydrochloric acid solution or both.
The addition of acid solution is calculated as 5~20mL/g with rice hull ash quality described in step (1) of the present invention.
Further, acid solution of the present invention is the mixed acid of hydrochloric acid, sulfuric acid or both, and hydrochloric acid is molten in the mixed acid
Liquid is 1 with the volume ratio of sulfuric acid solution：0.2~5.
Further, the addition of alkaline solution described in step (2) of the present invention be calculated as 5 with the quality of solid product~
15mL/g。
Further, aqueous slkali described in step (2) of the present invention be recommended as sodium hydroxide solution, sodium carbonate liquor or the two
Mixed-alkali solution, the substance withdrawl syndrome of the sodium hydroxide solution is 0.1~10mol/L, the sodium carbonate liquor
Substance withdrawl syndrome is 0.1~5mol/L, the volume of sodium hydroxide solution and sodium carbonate liquor in the mixed-alkali solution
Than being 1:0.1~10.
Hot water temperature described in step (2) of the present invention is 60~100 DEG C.
Generally, the addition volume of hot water is equal with the addition volume of aqueous slkali described in step (2) of the present invention.
Further, in step (3) of the present invention, when the liquid-phase precipitation agent is hydrochloric acid solution or sulfuric acid solution, liquid phase is sunk
The substance withdrawl syndrome of shallow lake agent is 0.1~5mol/L.
Further, in step (3) of the present invention, the liquid-phase precipitation agent is the mixed acid of hydrochloric acid solution and sulfuric acid solution
When, hydrochloric acid solution is 1 with the volume ratio of sulfuric acid solution:0.2~5.
Hydrochloric acid solution of the present invention, sulfuric acid solution, sodium hydroxide solution, sodium carbonate liquor all add in form of an aqueous solutions
Enter.
In step (3) of the present invention, described surfactant is recommended as Tween-80, neopelex, dodecane
Base sodium sulphate, cetyl trimethylammonium bromide or calgon.
Further, surfactant of the present invention mass fraction in mixed liquor is 0.05~5wt%.
Beneficial effect acquired by the present invention：Waterglass is extracted from rice hull ash, reduces cost is utilized to waste material, subtracted
Few pressure to environment；Using supergravity reactor stabilization, powerful Elevated Gravity, mass transport process and micro- is greatly enhanced
Mixing, the special efficacy of microreaction effect are seen, rational control sulfuric acid adds speed；Make sulfuric acid precipitation reaction using revolving bed characteristic
Waterglass and sulfuric acid moment reach good mixing, controlling the pH of mixed liquor makes it not produce gel, improves conversion ratio, makes to sink
The time of shallow lake reaction greatly shortens, and shortens the production cycle.The final nano SiO 2 particle prepared according to this method
Particle diameter is 10~100nm, and the scope of its application is than wide.It can be filled out as the additive of alkyd resin, rubber, plastics
Fill reinforcing agent, coating, insulation and thermal insulation filler, daily-use chemical industry raw material, the anticaking agent of agricultural chemicals medicine and carrier etc..
Brief description of the drawings
Fig. 1 is the TEM figures of the gained silicon-dioxide powdery of present example 1.
Fig. 2 is the SEM figures of the gained silicon-dioxide powdery of present example 1.
Fig. 3 is the infrared spectrum of the gained silicon-dioxide powdery of present example 1.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
The raw materials used rice hull ash produced from bio-power plant, composition analysis result such as following table in example：
Table 1 tests the composition analysis result of rice hull ash used
Embodiment 1
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the hydrochloric acid solution that 10mL/g pours into 1L 1mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water and reacts
2h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained everywhere
Rice hull ash after reason is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 5mL/g and pours into 150mL 3mol/L NaOH solutions, and condensation reflux unit is filled on there-necked flask, is placed in
4h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 85 DEG C of deionized waters of 150mL, merging filtrate, as water glass
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 1.507g 12 in 500mL there-necked flasks in weighing 300g steps (2)
Sodium alkyl benzene sulfonate (SDBS), stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 2.5mol/L sulfuric acid solutions, while being passed through
Being preheated in 75 DEG C of revolving bed carries out acidification reaction, and it is 3 to add the ratio between the waterglass after SDBS and sulfuric acid flow velocity:14, add
Waterglass flow velocity after SDBS is 33L/h.Revolving bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH to 8-9, ageing is added dropwise
30min.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, deionized water is washed to neutrality, and 150 DEG C are done
It is dry, crush the nano SiO 2 particle that can obtain average grain diameter 50nm, its TEM figures, SEM figures, infrared spectrum such as Fig. 1-3 institutes
Show, XRF constituent analyses are as shown in table 2.
The gained nano SiO 2 particle XRF constituent analyses of table 2
Embodiment 2
(1) weigh rice hull ash after 50g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice hull ash quality
The hydrochloric acid solution that 20mL/g pours into 1L 0.1mol/L is calculated as, condensation reflux unit is filled on there-necked flask, be placed in boiling water and react
5h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained everywhere
Rice hull ash after reason is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 5mL/g and pours into 150mL 10mol/L NaOH solutions, and condensation reflux unit is filled on there-necked flask, is placed in
1h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 60 DEG C of deionized waters of 150mL, merging filtrate, as water glass
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 0.1501g to tell in 500mL there-necked flasks in weighing 300g steps (2)
Temperature -80, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 5mol/L sulfuric acid solutions, while being passed through the rotation for being preheated to 75 DEG C
Acidification reaction is carried out in bed, it is 1 to add the ratio between waterglass and sulfuric acid flow velocity after Tween-80:1, add the water glass after Tween-80
Glass flow velocity is 60L/h.Revolving bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH to 8-9 is added dropwise, and is aged 15min.Question response
Terminate, the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, deionized water washed to neutrality, 150 DEG C dry, pulverize by obtain
Obtain the nano SiO 2 particle of average grain diameter 50nm.
Embodiment 3
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the hydrochloric acid solution that 8mL/g pours into 0.8L 1mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water anti-
Answer 3h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained
Rice hull ash after treatment is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 8mL/g and pours into 240mL 0.1mol/L Na2CO3Solution, fills condensation reflux unit on there-necked flask, puts
5h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 75 DEG C of deionized waters of 240mL, merging filtrate, as water
Glass solution, remains acid precipitation method standby.
(3) obtained water glass solution adds 4.444g 12 in 500mL there-necked flasks in weighing 400g steps (2)
Sodium alkyl sulfate (SDS), stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 3mol/L sulfuric acid solutions, while be passed through being preheated to
Acidification reaction is carried out in 75 DEG C of revolving bed, it is 2 to add the ratio between waterglass and sulfuric acid flow velocity after SDS:13, after adding SDS
Waterglass flow velocity is 48L/h.Revolving bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH to 9-10 is added dropwise, and is aged 60min.
Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 1-2.Filtering, deionized water is washed to neutrality, and 150 DEG C dry, pulverize
The nano SiO 2 particle of average grain diameter 50nm can be obtained.
Embodiment 4
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the hydrochloric acid solution that 5mL/g pours into 0.5L 5mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water anti-
Answer 1h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained
Rice hull ash after treatment is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 15mL/g and pours into 450mL 0.1mol/L NaOH solutions, and condensation reflux unit is filled on there-necked flask, puts
5h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 100 DEG C of deionized waters of 450mL, merging filtrate, as water
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 21.05g 16 in 500mL there-necked flasks in weighing 400g steps (2)
Alkyl trimethyl ammonium bromide, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 0.1mol/L sulfuric acid solutions, while being passed through pre-
Heat to acidification reaction is carried out in 75 DEG C of revolving bed, add waterglass and sulfuric acid flow velocity after cetyl trimethylammonium bromide it
Than being 1:3, it is 48L/h to add the waterglass flow velocity after cetyl trimethylammonium bromide.Revolving bed efflux is placed in 75 DEG C of water
In bath, ammoniacal liquor regulation pH to 8-9 is added dropwise, is aged 120min.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Cross
Filter, deionized water washed to neutrality, 150 DEG C dry, pulverize can acquisition average grain diameter 50nm nano SiO 2 particle.
Embodiment 5
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the hydrochloric acid solution that 10mL/g pours into 1L 1mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water and reacts
3h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained everywhere
Rice hull ash after reason is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 5mL/g and pours into 150mL 6mol/L NaOH solutions, and condensation reflux unit is filled on there-necked flask, is placed in
3h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 80 DEG C of deionized waters of 150mL, merging filtrate, as water glass
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 3.030g six inclined in 500mL there-necked flasks in weighing 300g steps (2)
Sodium phosphate, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 3mol/L sulfuric acid solutions, while being passed through the rotation for being preheated to 75 DEG C
Acidification reaction is carried out in rotated bed, it is 1 to add the ratio between waterglass and sulfuric acid flow velocity after calgon:1, add calgon
Waterglass flow velocity afterwards is 48L/h.Revolving bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH to 8-9, ageing is added dropwise
45min.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, deionized water is washed to neutrality, and 150 DEG C are done
It is dry, crush the nano SiO 2 particle that can obtain average grain diameter 50nm.
Embodiment 6
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the hydrochloric acid solution that 10mL/g pours into 1L 3mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water and reacts
3h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained everywhere
Rice hull ash after reason is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 10mL/g and pours into 300mL 0.5mol/L NaOH solutions, and condensation reflux unit is filled on there-necked flask, puts
4h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 85 DEG C of deionized waters of 300mL, merging filtrate, as water
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 8.163g 16 in 500mL there-necked flasks in weighing 400g steps (2)
Alkyl trimethyl ammonium bromide, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 1mol/L sulfuric acid solutions, while being passed through preheating
Acidification reaction is carried out into 75 DEG C of revolving beds, it is 1 to add the ratio between cetyl trimethylammonium bromide waterglass and sulfuric acid flow velocity:
1, it is 60L/h to add the waterglass flow velocity after cetyl trimethylammonium bromide.Revolving bed efflux is placed in 75 DEG C of water-baths, drop
Ammonification water adjusts pH to 8-9, is aged 45min.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, go from
Sub- water washing to neutrality, 150 DEG C dry, pulverize by obtain the nano SiO 2 particle of average grain diameter 50nm.
Embodiment 7
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the hydrochloric acid solution that 10mL/g pours into 1L 3mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water and reacts
3h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained everywhere
Rice hull ash after reason is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 15mL/g and pours into 450mL 10mol/L NaOH solutions, and condensation reflux unit is filled on there-necked flask, puts
4h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 85 DEG C of deionized waters of 450mL, merging filtrate, as water
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 4.04g dodecanes in 500mL there-necked flasks in weighing 400g steps (2)
Base sodium sulphate, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 0.5mol/L sulfuric acid solutions, while be passed through being preheated to 75 DEG C
Revolving bed in carry out acidification reaction, it is 1 to add the ratio between the waterglass after lauryl sodium sulfate and sulfuric acid flow velocity:20, add
Waterglass flow velocity after lauryl sodium sulfate is 33L/h.Revolving bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH is added dropwise
To 8-9,45min is aged.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, deionized water is washed into
Property, 150 DEG C dry, pulverize by obtain the nano SiO 2 particle of average grain diameter 50nm.
Embodiment 8
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the sulfuric acid solution that 10mL/g pours into 1L 1mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water and reacts
3h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained everywhere
Rice hull ash after reason is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 5mL/g and pours into 150mL 10mol/L NaOH solutions, and condensation reflux unit is filled on there-necked flask, is placed in
4h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 60 DEG C of deionized waters of 150mL, merging filtrate, as water glass
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 0.1501g to tell in 500mL there-necked flasks in weighing 300g steps (2)
Temperature -80, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 5mol/L sulfuric acid solutions, while being passed through the rotation for being preheated to 75 DEG C
Acidification reaction is carried out in bed, it is 1 to add the ratio between waterglass and sulfuric acid flow velocity after Tween-80:1, add the water glass after Tween-80
Glass flow velocity is 60L/h.Revolving bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH to 8-9 is added dropwise, and is aged 15min.Question response
Terminate, the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, deionized water washed to neutrality, 150 DEG C dry, pulverize by obtain
Obtain the nano SiO 2 particle of average grain diameter 50nm.
Embodiment 9
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the sulfuric acid solution that 10mL/g pours into 1L 1mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water and reacts
3h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained everywhere
Rice hull ash after reason is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 5mL/g and pours into 150mL 5mol/L Na2CO3Solution, fills condensation reflux unit on there-necked flask, is placed in
4h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 60 DEG C of deionized waters of 150mL, merging filtrate, as water glass
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 0.1501g 12 in 500mL there-necked flasks in weighing 300g steps (2)
Sodium alkyl benzene sulfonate, stirring, dissolving is abundant, and with by 1:The 0.5mol/L sulfuric acid of 1 mixing and the mixed solution of 3mol/L hydrochloric acid
75 DEG C are preheated to respectively, acidification reaction is carried out while being passed through and being preheated in 75 DEG C of revolving bed, add neopelex
The ratio between rear waterglass and sulfuric acid flow velocity are 1:1, it is 60L/h to add the waterglass flow velocity after neopelex.Rotation
Bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH to 8-9 is added dropwise, and is aged 15min.Question response terminates, and is added dropwise 4mol/L's
Sulphur acid for adjusting pH is to 2-3.Filtering, deionized water washed to neutrality, and 150 DEG C dry, pulverize can acquisition average grain diameter 50nm
Nano SiO 2 particle.
Embodiment 10
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the sulfuric acid solution that 10mL/g pours into 1L 2mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water and reacts
2h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained everywhere
Rice hull ash after reason is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 5mL/g and pours into 150mL 3mol/L NaOH solutions, and condensation reflux unit is filled on there-necked flask, is placed in
4h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 85 DEG C of deionized waters of 150mL, merging filtrate, as water glass
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 1.507g 12 in 500mL there-necked flasks in weighing 300g steps (2)
Sodium alkyl benzene sulfonate, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with the hydrochloric acid solution of 4.5mol/L, while being passed through preheating
Acidification reaction is carried out into 75 DEG C of revolving beds, it is 3 to add the ratio between waterglass and sulfuric acid flow velocity after neopelex:
14, it is 33L/h to add the waterglass flow velocity after neopelex.Revolving bed efflux is placed in 75 DEG C of water-baths, is added dropwise
Ammoniacal liquor adjusts pH to 8-9, is aged 30min.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, deionization
Water washing to neutrality, 150 DEG C dry, pulverize by obtain the nano SiO 2 particle of average grain diameter 50nm.
Embodiment 11
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as 10mL/g and pours into 1L by volume 1:1 mixing 1mol/L hydrochloric acid and 0.5mol/L sulfuric acid mixed solutions, in there-necked flask
Upper dress condensation reflux unit, is placed in and 3h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with deionized, until washing
Wash to neutrality.Filter residue is taken, 120 DEG C of dryings, the rice hull ash after being processed is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 5mL/g and pours into 150mL 2.5mol/L Na2CO3Solution, fills condensation reflux unit on there-necked flask, puts
3h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 80 DEG C of deionized waters of 150mL, merging filtrate, as water
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 3.030g six inclined in 500mL there-necked flasks in weighing 300g steps (2)
Sodium phosphate, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 1mol/L hydrochloric acid solutions, while being passed through the rotation for being preheated to 75 DEG C
Acidification reaction is carried out in rotated bed, it is 1 to add the ratio between waterglass and sulfuric acid flow velocity after calgon:2, add calgon
Waterglass flow velocity afterwards is 48L/h.Revolving bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH to 8-9, ageing is added dropwise
45min.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, deionized water is washed to neutrality, and 150 DEG C are done
It is dry, crush the nano SiO 2 particle that can obtain average grain diameter 50nm.
Embodiment 12
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as 10mL/g and pours into 1L by volume 5:The 0.1mol/L hydrochloric acid of 1 mixing and the mixed solution of 0.5mol/L sulfuric acid, three
Condensation reflux unit is filled on mouth flask, is placed in and 5h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with deionized,
Until washing to neutrality.Filter residue is taken, 120 DEG C of dryings, the rice hull ash after being processed is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 5mL/g and pours into 150mL 5mol/L Na2CO3Solution, fills condensation reflux unit on there-necked flask, is placed in
4h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 70 DEG C of deionized waters of 150mL, merging filtrate, as water glass
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 0.1501g six inclined in 500mL there-necked flasks in weighing 300g steps (2)
Sodium phosphate, stirring, dissolving is abundant, and with by volume 5:The 1mol/L sulfuric acid of 1 mixing and the mixed solution point of 3mol/L hydrochloric acid
75 DEG C are not preheated to, acidification reaction is carried out while being passed through and being preheated in 75 DEG C of revolving bed, add the water glass after calgon
The ratio between glass and sulfuric acid flow velocity are 1:1, it is 60L/h to add the waterglass flow velocity after calgon.Revolving bed efflux is placed in 75
In DEG C water-bath, ammoniacal liquor regulation pH to 8-9 is added dropwise, is aged 15min.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-
3.Filtering, deionized water washed to neutrality, 150 DEG C dry, pulverize can acquisition average grain diameter 50nm silica nanometer
Grain.
Embodiment 13
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as 5mL/g and pours into 1L by volume 1:The 3mol/L hydrochloric acid of 5 mixing and the mixed solution of 1mol/L sulfuric acid, in there-necked flask
Upper dress condensation reflux unit, is placed in and 2h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with deionized, until washing
Wash to neutrality.Filter residue is taken, 120 DEG C of dryings, the rice hull ash after being processed is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 15mL/g and pours into 450mL 3mol/L NaOH solutions, and condensation reflux unit is filled on there-necked flask, is placed in
5h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with 100 DEG C of deionized waters of 450mL, merging filtrate, as water glass
Glass solution, insulation, remains acid precipitation method standby.
(3) obtained water glass solution adds 21.05g 16 in 500mL there-necked flasks in weighing 400g steps (2)
Alkyl trimethyl ammonium bromide, stirring, dissolving is abundant, and with by volume 1:The 0.1mol/L sulfuric acid and 1mol/L hydrochloric acid of 5 mixing
Mixed solution is preheated to 75 DEG C respectively, and acidification reaction is carried out while being passed through and being preheated in 75 DEG C of revolving bed, adds cetyl
The ratio between waterglass and sulfuric acid flow velocity after trimethylammonium bromide are 1:3, add the waterglass after cetyl trimethylammonium bromide
Flow velocity is 48L/h.Revolving bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH to 8-9 is added dropwise, and is aged 120min.Question response
Terminate, the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, deionized water washed to neutrality, 150 DEG C dry, pulverize by obtain
Obtain the nano SiO 2 particle of average grain diameter 50nm.
Embodiment 14
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as 10mL/g and pours into 1L by volume 1:The 1mol/L hydrochloric acid of 3 mixing and the mixed solution of 0.5L 0.5mol/L sulfuric acid,
Condensation reflux unit is filled on there-necked flask, is placed in and 3h is reacted in boiling water.Question response is filtered immediately after terminating, and is washed with deionized water
Wash, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings, the rice hull ash after being processed is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 5mL/g and pours into 150mL by volume 1:The 1mol/L Na of 10 mixing2CO3Solution and 3mol/L NaOH are molten
The mixed solution of liquid, fills condensation reflux unit on there-necked flask, is placed in and 3h is reacted in boiling water.Question response terminate after mistake immediately
Filter, is washed, merging filtrate, as water glass solution with 80 DEG C of deionized waters of 150mL, is incubated, and remains acid precipitation method standby.
(3) obtained water glass solution adds 3.030g six inclined in 500mL there-necked flasks in weighing 300g steps (2)
Sodium phosphate, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 3mol/L hydrochloric acid solutions, while being passed through the rotation for being preheated to 75 DEG C
Acidification reaction is carried out in rotated bed, it is 1 to add the ratio between waterglass and sulfuric acid flow velocity after calgon:2, add calgon
Waterglass flow velocity afterwards is 48L/h.Revolving bed efflux is placed in 75 DEG C of water-baths, and ammoniacal liquor regulation pH to 8-9, ageing is added dropwise
45min.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Filtering, deionized water is washed to neutrality, and 150 DEG C are done
It is dry, crush the nano SiO 2 particle that can obtain average grain diameter 50nm.
Embodiment 15
(1) weigh rice hull ash after 100g is crushed to be placed in 1L there-necked flasks, according to the addition of acid solution with rice husk grey matter
Amount is calculated as the hydrochloric acid solution that 5mL/g pours into 0.5L 5mol/L, and condensation reflux unit is filled on there-necked flask, is placed in boiling water anti-
Answer 1h.Question response is filtered immediately after terminating, and is washed with deionized, until washing to neutrality.Filter residue is taken, 120 DEG C of dryings are obtained
Rice hull ash after treatment is standby.
(2) rice hull ash is placed in 500mL there-necked flasks after weighing 30g treatment, according to the addition of alkaline solution with solid
The quality of product is calculated as 15mL/g and pours into 0.5L by volume 10：The 2.5mol/L Na of 1 mixing2CO3Solution and 0.5mol/L
The mixed solution of NaOH solution, fills condensation reflux unit on there-necked flask, is placed in and 5h is reacted in boiling water.Question response stands after terminating
Filter, washed with 100 DEG C of deionized waters of 450mL, merging filtrate, as water glass solution, be incubated, remain acid precipitation method
It is standby.
(3) obtained water glass solution adds 21.05g 16 in 500mL there-necked flasks in weighing 400g steps (2)
Alkyl trimethyl ammonium bromide, stirring, dissolving is abundant, and is preheated to 75 DEG C respectively with 0.1mol/L sulfuric acid solutions, while being passed through pre-
Heat to acidification reaction is carried out in 75 DEG C of revolving bed, add waterglass and sulfuric acid flow velocity after cetyl trimethylammonium bromide it
Than being 1:3, it is 48L/h to add the waterglass flow velocity after cetyl trimethylammonium bromide.Revolving bed efflux is placed in 75 DEG C of water
In bath, ammoniacal liquor regulation pH to 8-9 is added dropwise, is aged 120min.Question response terminates, and the sulphur acid for adjusting pH of 4mol/L is added dropwise to 2-3.Cross
Filter, deionized water washed to neutrality, 150 DEG C dry, pulverize can acquisition average grain diameter 50nm nano SiO 2 particle.
Claims (10)
1. a kind of preparation method of nano SiO 2 particle, it is characterised in that described method is：
(1) to acid solution is added in rice hull ash, rice hull ash is immersed in described acid solution, be heated to reflux 1~5 hour, use
Dry solid product after neutrality is washed to, the substance withdrawl syndrome of the acid is 0.1~5mol/L；
(2) to alkaline solution is added in step (1) gained solid product, it is heated to reflux 1~5 hour, after reaction terminates, suction filtration,
And use hot wash filter residue, and the filtrate for obtaining as water glass solution is incubated standby, and the alkaline solution concentration is 0.1~
10mol/L；
(3) surfactant is added in the water glass solution of step (2) acquisition and obtains mixed liquor, then by mixed liquor and liquid
The flow-rate ratio of phase precipitating reagent is 1:1~20 is simultaneously passed through the mixed liquor after preheating and liquid-phase precipitation agent high-gravity rotating bed, obtains
Slurries, PH conditioning agents are made with ammoniacal liquor, adjust PH to 8-10, insulation 0.25~2h of ageing, and PH conditioning agents are made with sulfuric acid, regulation PH to
1-3, then filters, and gained filter cake is washed with water to neutrality, and heat drying, powder obtained by after crushing is silica nanometer
Grain；The liquid-phase precipitation agent is sulfuric acid solution, hydrochloric acid solution or the mixed acid of the two.
2. a kind of preparation method of nano SiO 2 particle as claimed in claim 1, it is characterised in that：Institute in step (1)
State the addition of acid solution and 5~20mL/g is calculated as with rice hull ash quality.
3. a kind of preparation method of nano SiO 2 particle as claimed in claim 1, it is characterised in that：Institute in step (1)
It is the mixed acid of hydrochloric acid solution, sulfuric acid solution or both to state acid solution, the body of hydrochloric acid solution and sulfuric acid solution in the mixed acid
Product is than being 1：0.2~5.
4. a kind of preparation method of nano SiO 2 particle as claimed in claim 1, it is characterised in that：Institute in step (2)
State the addition of alkaline solution and 5~15mL/g is calculated as with the quality of solid product.
5. a kind of preparation method of nano SiO 2 particle as claimed in claim 1, it is characterised in that：Institute in step (2)
Alkaline solution is stated for sodium hydroxide solution, sodium carbonate liquor or the mixed-alkali solution of the two, the thing of the sodium hydroxide solution
The amount concentration of matter is 0.1~10mol/L, and the substance withdrawl syndrome of the sodium carbonate liquor is 0.1~5mol/L, the mixed base
Property solution in the volume ratio of sodium hydroxide solution and sodium carbonate liquor be 1:0.1~10.
6. a kind of preparation method of nano SiO 2 particle as claimed in claim 1, it is characterised in that：Institute in step (2)
Hot water temperature is stated for 60~100 DEG C.
7. a kind of preparation method of nano SiO 2 particle as claimed in claim 1, it is characterised in that：In step (3), institute
When stating liquid-phase precipitation agent for hydrochloric acid solution or sulfuric acid solution, the substance withdrawl syndrome of liquid-phase precipitation agent is 0.1~5mol/L.
8. a kind of preparation method of nano SiO 2 particle as claimed in claim 1, it is characterised in that：In step (3), institute
State liquid-phase precipitation agent for hydrochloric acid solution and sulfuric acid solution mixed acid when, hydrochloric acid solution is 1 with the volume ratio of sulfuric acid solution:0.2
~5.
9. a kind of preparation method of nano SiO 2 particle as claimed in claim 1, it is characterised in that：In step (3), institute
The surfactant stated is Tween-80, neopelex, lauryl sodium sulfate, cetyl trimethylammonium bromide
Or calgon.
10. a kind of preparation method of nano SiO 2 particle as claimed in claim 1, it is characterised in that：In step (3),
Surfactant mass fraction in mixed liquor is 0.1~5wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108529636A (en) * | 2018-05-31 | 2018-09-14 | 佛山市高明区爪和新材料科技有限公司 | A kind of preparation method of Aerosil 200 micro mist |
| CN109201006A (en) * | 2018-09-03 | 2019-01-15 | 中成未来新材料（福建）有限公司 | A kind of environmental-protection adsorption material and preparation method thereof based on burning ash |
| CN112960677B (en) * | 2021-04-01 | 2021-10-26 | 广州市飞雪材料科技有限公司 | Precipitation method for preparing oral silicon dioxide with high oil absorption value and low viscosity |
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| CN1288856A (en) * | 2000-11-14 | 2001-03-28 | 北京化工大学 | Carbonization process to prepare nanometer silica |
| CN1394803A (en) * | 2002-07-31 | 2003-02-05 | 满金声 | Process for preparing nano silicone dioxide by adopting two-step carbonization reaction |
| CN1769166A (en) * | 2004-10-26 | 2006-05-10 | 北京化工大学 | Method for preparing superfine silicon dioxide powder using sulfuric acid precipitation reaction |
| CN1792789A (en) * | 2006-01-06 | 2006-06-28 | 哈尔滨工业大学 | Process for preparing nano silicon dioxide by rice straw ash |
| CN101391778A (en) * | 2008-10-09 | 2009-03-25 | 江南大学 | Method for preparing high-purity siliceous reinforcing agent by using rice hull ash as raw material |
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| CN1288856A (en) * | 2000-11-14 | 2001-03-28 | 北京化工大学 | Carbonization process to prepare nanometer silica |
| CN1394803A (en) * | 2002-07-31 | 2003-02-05 | 满金声 | Process for preparing nano silicone dioxide by adopting two-step carbonization reaction |
| CN1769166A (en) * | 2004-10-26 | 2006-05-10 | 北京化工大学 | Method for preparing superfine silicon dioxide powder using sulfuric acid precipitation reaction |
| CN1792789A (en) * | 2006-01-06 | 2006-06-28 | 哈尔滨工业大学 | Process for preparing nano silicon dioxide by rice straw ash |
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| CN108529636A (en) * | 2018-05-31 | 2018-09-14 | 佛山市高明区爪和新材料科技有限公司 | A kind of preparation method of Aerosil 200 micro mist |
| CN109201006A (en) * | 2018-09-03 | 2019-01-15 | 中成未来新材料（福建）有限公司 | A kind of environmental-protection adsorption material and preparation method thereof based on burning ash |
| CN112960677B (en) * | 2021-04-01 | 2021-10-26 | 广州市飞雪材料科技有限公司 | Precipitation method for preparing oral silicon dioxide with high oil absorption value and low viscosity |
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