CN100383041C - Method of preparing nanometer SiO2 from ophiolite - Google Patents
Method of preparing nanometer SiO2 from ophiolite Download PDFInfo
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- CN100383041C CN100383041C CNB2006100307509A CN200610030750A CN100383041C CN 100383041 C CN100383041 C CN 100383041C CN B2006100307509 A CNB2006100307509 A CN B2006100307509A CN 200610030750 A CN200610030750 A CN 200610030750A CN 100383041 C CN100383041 C CN 100383041C
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- nanometer sio
- sio
- leaching
- water
- solid residue
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Abstract
The present invention is superior process of preparing nanometer SiO2 with serpentine. Serpentine powder is first refluxed and leached to leach out soluble metal ions and solid matter with porous SiO2 as main component; and the solid matter is further prepared into nanometer SiO2 through a silicon tetrafluoride and sodium silicate process. The present invention has low cost and simple technological process.
Description
Technical field
The present invention relates to a kind of preparation of nanomaterials, particularly relate to a kind of nanometer SiO
2The preparation method.
Background technology
Nanometer is length metering unit (1m part per billion).The powder aggregate that the material grains diameter is in 1-100nm is called nanoparticle, it not only has big specific surface area, and surface atom number, surface energy and surface tension sharply increase with the decline of particle diameter, only just can observe its particle form under the high power electron microscope usually.
Nanometer SiO
2Being unformed white powder (referring to its coacervate), is a kind of nontoxic, tasteless, free of contamination ceramic.Its molecularity is three-dimensional chain-like structure (or claiming tridimensional network, three-dimensional silica stone structure etc.), the surface exist undersaturated residual bond and different bonding states through base, this makes SiO
2Nanoparticle has high surfactivity.Adopt the U.S. Cary-SE of Varian company sub-ray spectrometer to nanometer SiO
2Sample testing shows that to wavelength 200～280nm UV-light short-wave band, reflectivity is 70%-80%; To wavelength 280-300nm ultraviolet medium wave band, reflectivity is more than 80%; Between wavelength 300-800nm, nanometer SiO
2The luminous reflectance factor of material reaches 85%; Wavelength is also reached 70%～80% at the near infrared light reflectivity of 800～1300nm.Therefore, its special optical performance of having.Nanometer SiO
2Volume effect and quantum tunneling effect make it produce trip to ooze effect, the people is near two keys of macromolecular compound deeply, overlap with its electronic cloud, form the space reticulated structure, thereby increased substantially mechanical strength, toughness, wear resistance and the ageing resistance etc. of macromolecular material.Thereby people often utilize nanometer SiO
2These special constructions and performance plastics and coating are carried out modification or prepare organic SiO
2Matrix material, the over-all properties of raising organic polymer material.
Nanometer SiO
2Small-size effect, surface and interfacial effect, quantum size effect and macro quanta tunnel effect etc. have caused nanoparticle to have unusual or unusual physicals and chemical property, thereby its many fields in electronics, chemical industry, the energy, biology, medicine, agricultural and daily life are widely used.Prepare nanometer SiO at present
2Main method is as follows:
(1) vapor phase process:
Laser active chemical vapour deposition (LICVD) is preparation nanometer SiO
2One of effective ways.This method ratio is easier to prepare crystalline state and amorphous nano particles, but has cleaning, wall-less effect, even particle size distribution, nothing bonding, output height continuous production and advantage such as be widely used.In order to obtain high pure and ultra-fine SiO
2Powder utilizes SiCl in the technology
4Phase feed reacts after activating as reactant, and its chemical equation is:
SiCl
4↑+O
2↑＝SiO
2+2Cl
2↑
For making full use of SiCl
4, O
2With SiCl
4General ratio of mixture was at least 4: 1.Simultaneously, react completely thoroughly for making, unstripped gas should be from being passed by the quartz pushrod facular area of laser radiation, so that react from the rod heat absorption.In temperature is 1120～1200 ℃, and oxygen flow is 0.5～1.0L/min, SiCl
4Gas flow is 0.172～0.345L/min, and when laser power was 3000～350W, 15min just can generate SiO
2Nanometer powder.But there is the raw materials cost height in this side, and shortcoming such as yield poorly.
(2) azeotropic distn:
In 30 ℃ ± 1 ℃ isothermal reactor, certain density water glass (modulus 3.34) and ethyl acetate are mixed by a certain percentage, after reaction forms gel, adjust pH=4.0, filter and be washed with distilled water to filtrate and can not detect Cl with AgNO3 with 1: 1 hydrochloric acid
-Gel after the washing and a certain amount of propyl carbinol mix, and carry out component distillation under 93 ℃.When system boiling point during by 117 ℃ of 93 ℃ of boiling points that are elevated to propyl carbinol itself gradually, the water in the gel is removed fully.After continuing backflow 30min under this temperature, steam propyl carbinol, and will distill back gained gel in baking oven in 120 ℃ of dry 2h, promptly get the SiO of very loose nothing reunion
2Nanometer powder, its grain diameter are 20～40nm.Ethyl acetate among this side and the cost of propyl carbinol is higher and large usage quantity is difficult to realize suitability for industrialized production.
(3) teos hydrolysis method:
This method is the source material with tetraethoxy (TEOS), and high-quality pure dehydrated alcohol (EtoH) is a solvent, and distilled water is promotor, and hydrochloric acid, phosphoric acid, polyoxyethylene glycol etc. are additive.The solvent of half amount is mixed with TEOS earlier, to be mixed with the water mixed liquid that contains of partly measuring solvent in addition again mixes with it, under violent induction stirring condition, drip people TEOS solution, make it that hydrolysis reaction take place, then allow its abundant polycondensation at a certain temperature, form gel, the gained wet gel is placed loft drier, dry down at 60 ℃, get xerogel at last, xerogel grinds and disperses rearmounted people's retort furnace through ultrasonic oscillation, further respectively at 300 ℃, and 450 ℃, 700 ℃ of following sintering promptly get nanometer SiO
2Powder.Measurement shows to size, and 300 ℃, 450 ℃, the median size of 700 ℃ of sintered samples is respectively 14nm, 21nm and 30nm.If temperature surpasses 1000 ℃, then do not belong to nano material substantially.Higher and the large usage quantity of the cost of the tetraethoxy among this side is difficult to realize suitability for industrialized production.
(4) the carbonization precipitator method:
This method is 3.1～3.4 with modulus, density 1.3835kg/L, SiO
2Content is that 27%～28% water glass and purity are higher than 99% CO
2Gas is raw material.At first, certain density water glass solution left standstill to filter be placed in the supergravity reactor, be warming up to temperature of reaction after, add people's flocculation agent and tensio-active agent, open rotating packed bed and feed liquid recycle pump, stir and reflux.After treating temperature-stable, logical people CO
2Gas reacts, and stops air inlet behind the pH value stabilization, finishes reaction.Add sour pH value and transfer to preset value feed liquid, and the insulation ageing.After the ageing, suction filtration and washing at 110～160 ℃ of down dry 6.0～7.0h, are ground at last, are sieved, and promptly get ultra-fine SiO
2Pulverized structure.Silicon dioxide granule size with this method preparation is even, and median size is amorphous structure less than 30nm.Owing to be reflected in the hypergravity environment and carry out, so mass transfer process and micro mixing have obtained very big reinforcement, have shortened the reaction times greatly.Use ball-milling technology in this method, can increase technology difficulty and cost to a certain extent.
(5) chemical precipitation method:
Na 19%
2SiO
3In the solution, drip 1.2molL
-HCI solution carries out precipitin reaction, and when the pH=8 left and right sides, adds people 5% nonionogenic tenside P.Be reflected in the water-bath and carry out, and controlled temperature is about 50 ℃.The gained throw out is washed 6～7 times with centrifuging, to remove wherein Cl
-Ion, in microwave oven about dry 20min, at last in retort furnace with optimal temperature (470～500 ℃) thermal treatment 1h, promptly obtain nanometer SiO
2Powder.This powder is a form of spherical particles, even particle size distribution, and particle diameter is less, and is distributed with many micropores in each particle, and its aperture is very little, and mean pore size is about 25 goes into, and the shared total area of micropore reaches 800cm
2More than/the g, inner ratio surface area accounts for more than 76% of total specific surface area.That this side adopts is industrial inorganic raw material Na
2SiO
3Solution, if can use raw mineral materials cheaply, chemical precipitation method is to be hopeful large-scale production most so.
China's serpentinite (contains 30～40%SiO
2) characteristics such as Mineral resources are very abundant, mostly are the serpentinite mineral deposits of ultrabasic rocks type, and it is many to have a mineral deposit, and that rule are touched is big, it is wide to distribute, the quality condition is good.Place surplus the serpentinite mining area 50 of whole nation discovery and proven reserve mainly is distributed in province, districts such as Hebei, Jiangxi, Sichuan, the Inner Mongol, Heilungkiang, Jiangsu, Anhui, Fujian, Shandong, Henan, Hubei, Guangdong, Yunnan, Guangxi, Shaanxi, Gansu, Qinghai, Xinjiang.These provinces, district all have large-scale and medium-sized mineral deposit to distribute, and have verified nearly 12,000,000,000 t of serpentinite ore reserves.
Summary of the invention
At existing preparation nanometer SiO
2The part that comes with some shortcomings in the technology causes nanometer SiO
2Production cost height, complex process, and be unfavorable for nanometer SiO
2Large-scale production.According to hydrometallurgy and chemical principle, take concentrated hydrochloric acid to reflux and leach the serpentine breeze, the soluble metal ion in the serpentine is leached (Mg2+Fe3+, Ni2+, Al3+, Ca2+), remaining solid residue main component is porous SiO
2, get nanometer SiO2 by employing silicon tetrafluoride and water glass legal system respectively then, thereby realization is low-cost, technology is produced nanometer SiO easily
2
The inventive method adopts serpentine minerals feedstock production nanometer SiO
2Powder, with returned acid (as concentrated hydrochloric acid) leaching serpentine breeze, solid-to-liquid ratio is controlled between 1: 3～1: 4,75～95 ℃ of temperature controls, time is 1 hour, have high-content Mg2+ ion and a spot of Fe3+, Ni2+, Al3+, Ca2+ impurity element in the leaching liquid, leaching liquid will be handled with abstraction technique.The main component of the solid residue after the leaching is a porous silica, and washes solid residue with water.Solid residue adopts following two kinds of methods to produce nanometer SiO
2
1. with silicon fluoride production nanometer SiO
2
The solid residue of above-mentioned washes clean and hydrofluoric acid reaction generate SiF4, silicon tetrafluoride gas is fed different concns, and (mol ratio of ethanol and deionized water was not less than 3: 1, be not higher than 5: 1) ethanol and the mixing solutions of water in, filter then, place the baking oven oven dry promptly to obtain nanometer SiO the filter cake after filtering
2Product
2. the slag of crossing with 15～20% sodium hydroxide solution backflow carrying out washing treatment is produced water glass (Na2SiO3), and its productive rate can reach more than 95%, and above-mentioned water glass is produced nanometer SiO by the salt acid precipitation method
2The fineness of serpentine breeze is 80 orders, refluxes with 31% technical hydrochloric acid and leaches breeze in 1 hour, and liquid-solid ratio is 3: 1～4: 1, and reflux temperature is controlled at 75～95 ℃.Feed liquid after the leaching will be handled with extraction process, and the solid residue after the leaching washes with water and is used to prepare nanometer SiO
2
(1) with silicon fluoride production nanometer SiO
2
The solid residue of above-mentioned washes clean and hydrofluoric acid reaction generate SiF4, and its reaction equation is as follows:
SiO
2+4HF＝2H
2O+SiF4↑
Above-mentioned a certain amount of silicon tetrafluoride gas is fed different concns, and (mol ratio of ethanol and deionized water was not less than 3: 1, be not higher than 5: 1) ethanol and the mixing solutions of water in, behind the ageing 4h, filter, wash to filtrate pH value between 6～7, filter cake is placed baking oven,, get nanometer SiO at 150 ℃ of baking 24h
2Product.If the mol ratio of above-mentioned ethanol and deionized water is lower than at 3: 1 o'clock, the SiO2 particle is grown up rapidly, so just can not get nanometer SiO2 product.
Silicon tetrafluoride experiences following process in the mixed solvent of second alcohol and water:
SiF4↑+xH
2O+(4-x)CH3CH2OH→Si(OH)4CH3CH2OH(4-x)+4HF
Si(OH)4CH3CH2OH(4-x)→SiO
2+H
2O+CH3CH2OH
(2) slag of crossing with 16% sodium hydroxide solution backflow carrying out washing treatment is produced water glass (Na2SiO3), and its productive rate can reach more than 95%.Produce nanometer SiO with salt Acid precipitation soluble glass method
2The pH value of solution is controlled at 7～9, adds dilute NaOH solution and alkyls tensio-active agent in the hydrochloric acid precipitation process, stops the SiO in the water glass like this
2Particle accumulation is grown up.In stoving process process auxiliary ultrasonic, so also can prevent SiO
2Particle aggregation.
Beneficial effect of the present invention:
1. adopt serpentine to produce nanometer SiO2, thereby reach the effect of reclamation of solid wastes.
2. the characteristics with silicon fluoride production nanometer SiO2 are that HF and ethanol can recycle, and do not pollute thereby can not produce environment.
3. silicon fluoride and water glass legal system are got nanometer SiO
2Technology simple, production cost is low.
Embodiment
Embodiment 1
Take by weighing the solid residue of a certain amount of 100g, add excessive hydrofluoric acid (excessive 10%), temperature of reaction is controlled at room temperature, the SiF4 gas that produces is passed in the aqueous ethanolic solution behind (mol ratio of ethanol and deionized water is 3: 1) ageing 4h, filter, wash to filtrate pH value be 6, filter cake is placed baking oven, at 150 ℃ of baking 24h, get nanometer SiO2 product.
Embodiment 2
Take by weighing the solid residue of 100g, put into 16% sodium hydroxide solution and reflux, solid-to-liquid ratio was controlled at 1: 3, and reflux temperature is 80 ℃, and the reaction times is 1h.Reacted product is a water glass, hydrochloric acid, tensio-active agent is joined in the sodium silicate solution again, can obtain the silicic acid precipitation like this, dries under the ultrasonic wave condition again, promptly obtains nanometer SiO2 product.
Embodiment 3
Take by weighing 150g, the serpentine breeze of 80 order fineness is a raw material, and with 31% technical hydrochloric acid backflow 1h leaching breeze, liquid-solid ratio is 4: 1, and reflux temperature is controlled at 95 ℃.The leaching liquid that obtains is filtered, carry out solid-liquid separation, the solid of gained is the solid residue of producing nanometer SiO2.
Claims (7)
1. one kind prepares nanometer SiO from serpentine
2Method, it is characterized in that, with returned acid leaching serpentine breeze, solid-to-liquid ratio is controlled between 1: 3～1: 4,75～95 ℃ of temperature controls, and leaching liquid is handled with abstraction technique, the main component of the solid residue after the leaching is a porous silica, and solid residue and hydrofluoric acid reaction generate SiF
4, silicon tetrafluoride gas being fed in the mixing solutions of Different concentrations of alcohol and water, the mol ratio of ethanol and deionized water is 3～5: 1, filters then, places the baking oven oven dry promptly to obtain nanometer SiO the filter cake after filtering
2Product.
2. the method for claim 1 is characterized in that, described returned acid is a concentrated hydrochloric acid.
3. method as claimed in claim 1 or 2 is characterized in that, in the described mixing solutions that silicon tetrafluoride gas is fed described Different concentrations of alcohol and water, filters then, wash to filtrate pH value between 6～7.
4. method as claimed in claim 1 or 2 is characterized in that filter cake places baking oven, at 150 ℃ of baking 24h, gets nanometer SiO
2Product.
5. the method for claim 1 is characterized in that, produces water glass with the solid residue that sodium hydroxide solution refluxes after leaching, and produces nanometer SiO with salt Acid precipitation soluble glass method
2
6. method as claimed in claim 5, when it is characterized in that with salt Acid precipitation water glass, the pH value of solution is controlled at 7～9.
7. as claim 5 or 6 described methods, it is characterized in that, add some tensio-active agents in the hydrochloric acid precipitation process.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100307509A CN100383041C (en) | 2006-09-01 | 2006-09-01 | Method of preparing nanometer SiO2 from ophiolite |
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|---|---|---|---|
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| CN100383041C true CN100383041C (en) | 2008-04-23 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293655B (en) * | 2007-04-26 | 2011-04-20 | 侯振海 | Novel method for preparing high purity silicon dioxide |
| CN101428805B (en) * | 2008-12-03 | 2011-06-29 | 湖北永绍科技有限公司 | Utilization technology for fluorine-containing white residue |
| CN103922348A (en) * | 2014-04-17 | 2014-07-16 | 宁婷婷 | Method for preparing white carbon black by using serpentinite |
| CN105256151B (en) * | 2015-10-14 | 2017-07-21 | 上海大学 | The method that the magnesium chloride in serpentine is extracted with ethanol |
| CN105648211B (en) * | 2015-12-09 | 2017-12-22 | 上海大学 | The method of magnesium chloride in high temperature and high pressure method leaching serpentine |
| CN107827350B (en) * | 2017-11-15 | 2020-06-23 | 新沂市晶润石英材料有限公司 | Method for preparing glass by using quartz sand dust collected in ash hopper |
| CN110342530B (en) * | 2019-08-12 | 2022-12-20 | 中谱科技(福州)有限公司 | Mesoporous silica and preparation method thereof |
| CN112897530B (en) * | 2021-03-01 | 2022-10-14 | 内蒙古工业大学 | Method for efficiently dissolving silicate substances and extracting high-purity silicon oxide |
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