CN102515104B - Method for preparing hydrogen chloride and silicon dioxide by hydrolyzing silicon tetrachloride in organic solvent - Google Patents
Method for preparing hydrogen chloride and silicon dioxide by hydrolyzing silicon tetrachloride in organic solvent Download PDFInfo
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- CN102515104B CN102515104B CN 201210004568 CN201210004568A CN102515104B CN 102515104 B CN102515104 B CN 102515104B CN 201210004568 CN201210004568 CN 201210004568 CN 201210004568 A CN201210004568 A CN 201210004568A CN 102515104 B CN102515104 B CN 102515104B
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Abstract
The invention belongs to the field of chemical industry and particularly relates to a method for preparing hydrogen chloride and silicon dioxide by hydrolyzing silicon tetrachloride in an organic solvent. According to the method, the organic solvent is used as a medium, water is added into a mixed solution of silicon tetrachloride, the organic solvent and a surfactant to start a hydrolysis reaction to form hydrogen chloride and silicon dioxide, the formed hydrogen chloride gas is dried and recycled, and the silicon dioxide is sold after being washed by alcohol and dried. The method recycles the silicon tetrachloride and has the characteristics of high productivity, low energy consumption, small investment and the like.
Description
Technical field
The invention belongs to chemical field, relate to a kind of method that hydrolyzing silicon tetrachloride in organic solvent prepares hydrogenchloride and silicon-dioxide.
Background technology
Along with the super scale development of China's photovoltaic industry, the throughput of polysilicon reaches 90,000 ton/years.And 1 ton of polysilicon of every production produces by-product the silicon tetrachloride of 10-20 ton.The silicon tetrachloride of unprocessed recovery is a kind of poisonous and harmful liquid with severe corrosive, very large to safety and environmental hazard.How processing the huge silicon tetrachloride as by-product of quantity has become a great problem of production of polysilicon enterprise.
The digestion approach of silicon tetrachloride mainly contains three kinds at present: the one, and the thermal silica of preparation high added value; The 2nd, prepare trichlorosilane by hydrogenation; The 3rd, hydrolysis generates dilute hydrochloric acid and silicon-dioxide.The thermal silica added value is high, and purposes is wide, and preparing the thermal silica technology with silicon tetrachloride is effectively to utilize the Perfected process of silicon tetrachloride.But the white carbon black market capacity is limited, adopt merely the thermal silica technology can't digest the huge silicon tetrachloride of quantity.The Technology that the hydro-reduction silicon tetrachloride prepares trichlorosilane exists a shortcoming such as low conversion rate and greatly limits its application.Hydrolysis method is silicon tetrachloride to be reacted with water generate hydrogen chloride gas and silicon-dioxide.The hydrolysis method processing silicon chloride technique that Chinese patent CN101591018A proposes is reacted silicon tetrachloride and dilute hydrochloric acid and fresh water in reactor, generates hydrogen chloride gas and silicon-dioxide.It is simple that this technique has flow process, the advantage that the silicon tetrachloride treatment capacity is large, but this technique fresh water consumption is large; The silica dioxide gelization generated is serious, and water content is up to 80%, and drying obtains silicon-dioxide powdery need to consume a large amount of heats, and energy consumption is high, seriously affects quality and the class of product due to silica dioxide gelization simultaneously.
Summary of the invention
The present invention is directed to shortcoming of the prior art provides a kind of hydrolyzing silicon tetrachloride in organic solvent to prepare the method for hydrogenchloride and silicon-dioxide, the method can take full advantage of by product, the hydrogen chloride gas recoverable generated, and can directly obtain the low silicon-dioxide powdery of gelation, overcome in traditional hydrolysis method the fresh water consumption large, the shortcomings such as the serious and energy consumption height of dried silica gelation.
The present invention is achieved by the following technical programs:
A kind of hydrolyzing silicon tetrachloride in organic solvent of the present invention prepares the method for hydrogenchloride and silicon-dioxide, and it comprises the following steps:
At 0～50 ℃ of temperature, silicon tetrachloride and organic solvent and tensio-active agent are mixed with to mixing solutions, water is under agitation joined in described mixing solutions, reaction is hydrolyzed, generate silicon-dioxide and hydrogen chloride gas, after then precipitation of silica being filtered again with after methyl alcohol or washing with alcohol, drying, obtaining silicon-dioxide powdery.
Described organic solvent is one or both mixing containing in the aromatic hydrocarbons halides of 6-8 carbon.
Described tensio-active agent is a kind of in Sodium dodecylbenzene sulfonate or alkylphenol polyoxyethylene (OP-10).
The weight ratio of described tensio-active agent and silicon tetrachloride is 0.1～1: 10.
Described silicon tetrachloride and organic solvent volume ratio are 1.0～6.0: 10.0, and described water and silicon tetrachloride mol ratio are 2～2.5: 1.
Preferably, described a kind of hydrolyzing silicon tetrachloride in organic solvent prepares the method for hydrogenchloride and silicon-dioxide, and reaction process also comprises, the filtrate cycle after the filtration alcohol wash is used 10～15 times, then after carrying out rectifying and obtaining methyl alcohol or ethanol, then return and reuse.
Preferably, described a kind of hydrolyzing silicon tetrachloride in organic solvent prepares the method for hydrogenchloride and silicon-dioxide, and reaction process also comprises, the hydrogen chloride gas produced in described hydrolysis reaction is reclaimed after being introduced into follow-up drying installation drying.
Preferably, described a kind of hydrolyzing silicon tetrachloride in organic solvent prepares the method for hydrogenchloride and silicon-dioxide, and the hydrogen chloride gas of described recovery is for the production of trichlorosilane or PVC.
Preferably, described a kind of hydrolyzing silicon tetrachloride in organic solvent prepares the method for hydrogenchloride and silicon-dioxide, and described methyl alcohol or ethanol are anhydrous methanol or dehydrated alcohol.
Preferably, described a kind of hydrolyzing silicon tetrachloride in organic solvent prepares the method for hydrogenchloride and silicon-dioxide, the methyl alcohol that described methyl alcohol or ethanol are 95% or 95% ethanol.
The present invention compared with prior art, has the following advantages:
1. technical process is simple, and raw material is easy to get, and scale of investment is little.
2. in the recycling treatment process to silicon tetrachloride, with an organic solvent, with the water reaction that is hydrolyzed, wherein organic solvent can be recycled, and industrial running cost is low.
3. the present invention utilizes the polysilicon by-produced tetrachlorosilane to react the principle that generates hydrogenchloride and silicon-dioxide with water, using organic solvent as reaction medium, water and silicon tetrachloride are reacted and are generated solid silica by stoichiometric ratio with water termination at organic solvent, have avoided the existence of excessive water in traditional hydrolytic process to cause the generation of silica dioxide gel.This technique has overcome in the silica dioxide gel drying process that traditional hydrolysis method produces the serious and high shortcoming of energy consumption of gelation, and the hydrogen chloride gas recoverable point of generation.
In addition, tensio-active agent adds the reunion that has slackened silica dioxide granule.The silicon-dioxide quality that the present invention produces meets the industry standard requirement, reclaims the requirement that hydrogenchloride can meet trichlorosilane or PVC production fully.
Embodiment
Below by specific embodiment, the present invention is further illustrated:
Embodiment 1
In the time of 25 ℃, add the 1.3g Sodium dodecylbenzene sulfonate in the 250ml parachlorotoluene, the 30ml silicon tetrachloride; Under stirring, 2ml water slowly is added drop-wise in the silicon tetrachloride reaction solution of parachlorotoluene to the reaction that is hydrolyzed.The hydrogen chloride gas gas generated, by filtering, send trichlorosilane or PVC production equipment to use after drying treatment; Hydrolysis reaction carries out filtering separation by precipitation of silica in reactor after finishing, and parachlorotoluene filtration raffinate is put into container and collected, in order to recycling; The solid silica filtered out is under agitation 4 by 95% ethanol alcohol wash depickling to pH value, then filters, and drying obtains silicon-dioxide powdery.The specific surface area of gained silicon-dioxide is 185m
2/ g, particle diameter is 210nm.The ethanol that alcohol wash filters out returns and reuses after collecting.
Embodiment 2
In the time of 30 ℃, add 0.9g Surfactant OP-10 in the 200ml ortho-chlorotolu'ene, the 30ml silicon tetrachloride; Under stirring, 2ml water slowly is added drop-wise in the silicon tetrachloride reaction solution of ortho-chlorotolu'ene to the reaction that is hydrolyzed.The hydrogen chloride gas gas generated after filtration, send trichlorosilane or PVC production equipment to use after drying treatment; Hydrolysis reaction carries out filtering separation by precipitation of silica in reactor after finishing, and ortho-chlorotolu'ene filtration raffinate is put into container and collected, in order to recycling; The solid silica filtered out is under agitation 4 by 95% ethanol alcohol wash depickling to pH value, then filters, and drying obtains silicon-dioxide powdery.The specific surface area of gained silicon-dioxide is 162m
2/ g, particle diameter is 280nm.The ethanol that alcohol wash filters out returns and reuses after collecting.
Embodiment 3
In the time of 35 ℃, in 250ml parachlorotoluene and m-chlorotoluene (parachlorotoluene and m-chlorotoluene volume ratio are 1: 1) mixed solvent, add 1.2g Surfactant OP-10, the 30ml silicon tetrachloride; Under stirring, 2.2ml water slowly is added drop-wise in the silicon tetrachloride reaction solution of mixed solvent to the reaction that is hydrolyzed.The hydrogen chloride gas gas generated, by filtering, send trichlorosilane or PVC production equipment to use after drying treatment; After hydrolysis reaction finishes, precipitation of silica in reactor is carried out to filtering separation, parachlorotoluene and m-chlorotoluene filter and mix raffinate and put into container and collect, and prepare against and recycle; The solid silica filtered out is under agitation 4 by 95% ethanol alcohol wash depickling to pH value, then filters, and drying obtains silicon-dioxide powdery.The specific surface area of gained silicon-dioxide is 155m
2/ g, particle diameter is 200nm.The ethanol that alcohol wash filters out returns and reuses after collecting.
Claims (6)
1. a hydrolyzing silicon tetrachloride in organic solvent prepares the method for hydrogenchloride and silicon-dioxide, it is characterized in that it comprises the following steps:
At 0～50 ℃ of temperature, silicon tetrachloride and organic solvent and tensio-active agent are mixed with to mixing solutions, water is under agitation joined in described mixing solutions, reaction is hydrolyzed, generate silicon-dioxide and hydrogen chloride gas, after then precipitation of silica being filtered again with after methyl alcohol or washing with alcohol, drying, obtaining silicon-dioxide powdery;
Described organic solvent is one or both mixing containing in the aromatic hydrocarbons halides of 6-8 carbon; The described aromatic hydrocarbons halides containing 6-8 carbon is parachlorotoluene, ortho-chlorotolu'ene or m-chlorotoluene;
Described tensio-active agent is a kind of in Sodium dodecylbenzene sulfonate or alkylphenol polyoxyethylene;
The weight ratio of described tensio-active agent and silicon tetrachloride is 0.1～1:10;
Described silicon tetrachloride and organic solvent volume ratio are 1.0～6.0:10.0, and described water and silicon tetrachloride mol ratio are 2～2.5:1.
2. a kind of hydrolyzing silicon tetrachloride in organic solvent as claimed in claim 1 prepares the method for hydrogenchloride and silicon-dioxide, it is characterized in that:
Reaction process also comprises, the filtrate cycle of filtering after alcohol wash is used 10～15 times, after then carrying out rectifying and obtaining methyl alcohol or ethanol, then returns and reuses.
3. a kind of hydrolyzing silicon tetrachloride in organic solvent as claimed in claim 1 prepares the method for hydrogenchloride and silicon-dioxide, it is characterized in that:
Reaction process also comprises, the hydrogen chloride gas produced in described hydrolysis reaction is reclaimed after being introduced into follow-up drying installation drying.
4. a kind of hydrolyzing silicon tetrachloride in organic solvent as claimed in claim 3 prepares the method for hydrogenchloride and silicon-dioxide, it is characterized in that:
The hydrogen chloride gas of described recovery is for the production of trichlorosilane or PVC.
5. a kind of hydrolyzing silicon tetrachloride in organic solvent as claimed in claim 1 prepares the method for hydrogenchloride and silicon-dioxide, it is characterized in that:
Described methyl alcohol or ethanol are anhydrous methanol or dehydrated alcohol.
6. a kind of hydrolyzing silicon tetrachloride in organic solvent as claimed in claim 1 prepares the method for hydrogenchloride and silicon-dioxide, it is characterized in that:
The methyl alcohol that described methyl alcohol or ethanol are 95% or 95% ethanol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201210004568 CN102515104B (en) | 2012-01-09 | 2012-01-09 | Method for preparing hydrogen chloride and silicon dioxide by hydrolyzing silicon tetrachloride in organic solvent |
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| CN 201210004568 CN102515104B (en) | 2012-01-09 | 2012-01-09 | Method for preparing hydrogen chloride and silicon dioxide by hydrolyzing silicon tetrachloride in organic solvent |
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| CN102515104A CN102515104A (en) | 2012-06-27 |
| CN102515104B true CN102515104B (en) | 2013-12-18 |
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| CN103272362A (en) * | 2013-05-11 | 2013-09-04 | 乐山师范学院 | Method for detoxicating hexavalent chromium in chromium slag by using silicon tetrachloride |
| CN105965012B (en) * | 2016-06-07 | 2018-01-02 | 广州新莱福磁电有限公司 | A kind of method of soft-magnetic alloy powder body Surface coating silica insulation film layer |
| CN107970880B (en) * | 2018-01-19 | 2019-09-03 | 四川广阳环保科技有限公司 | A kind of preparation method of improved silica adsorbent |
| CN108059168B (en) * | 2018-01-19 | 2019-09-24 | 四川广阳环保科技有限公司 | A kind of method, product and purposes preparing improved silica adsorbent using chlorosilane raffinate |
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| CN1075154A (en) * | 1993-03-03 | 1993-08-11 | 复旦大学 | A kind of preparation method who is used for the filler-silicon dioxide of epoxy mold sealing material |
| JP2011046577A (en) * | 2009-08-28 | 2011-03-10 | Mitsubishi Materials Corp | Method for producing synthetic silica powder |
| CN102107855B (en) * | 2009-12-25 | 2014-03-26 | 王朝锋 | Method for producing hydrochloric acid and silicon dioxide by using silicon tetrachloride as raw material |
| CN102275940B (en) * | 2011-07-28 | 2013-01-23 | 河北东明中硅科技有限公司 | Method for low-temperature hydrolysis of silicon tetrachloride |
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