CN102583397A - Method for preparing silicon dioxide and hydrogen chloride by means of hydrolysis of polysilicon by-product silicon tetrachloride - Google Patents
Method for preparing silicon dioxide and hydrogen chloride by means of hydrolysis of polysilicon by-product silicon tetrachloride Download PDFInfo
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- CN102583397A CN102583397A CN2012100052577A CN201210005257A CN102583397A CN 102583397 A CN102583397 A CN 102583397A CN 2012100052577 A CN2012100052577 A CN 2012100052577A CN 201210005257 A CN201210005257 A CN 201210005257A CN 102583397 A CN102583397 A CN 102583397A
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Abstract
The invention relates to a method for preparing silicon dioxide and hydrogen chloride by means of hydrolysis of polysilicon by-product silicon tetrachloride. The method comprises the following steps of: adding additives and surfactants into an airtight reaction kettle with 5 to 30 mass percent of hydrochloric acid aqueous solution, adding the silicon tetrachloride into the airtight reaction kettle, wherein the input amount of the silicon tetrachloride is controlled to be between 0.4 and 0.9 m<3>/h; performing a hydrolysis reaction by controlling the temperature to be between 20 and 50 DEG C, and generating silica sol and hydrogen chloride gas; drying and recycling the hydrogen chloride gas; standing and aging the silica sol to form silicon dioxide precipitates; filtering and washing the silicon dioxide precipitates to remove the residual additives; and drying the washed silicon dioxide colloid, and thus obtaining precipitated white carbon black (silicon dioxide). The process has the characteristics of simple process flow, readily available raw materials, low production cost and the like.
Description
Technical field
The invention belongs to field of inorganic chemical engineering, relate to a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride.
Background technology
Silicon tetrachloride is the maximum by product of generation in the production of polysilicon, and the silicon tetrachloride of unprocessed recovery is a kind of poisonous and harmful liquid with severe corrosive, and is very big to safety and environmental hazard.2010, China's polysilicon output reached about 40,000 tons, and silicon tetrachloride as by-product is about 600,000 tons.The aftertreatment problem of a large amount of silicon tetrachlorides has become the bottleneck of restriction polysilicon industry development.
In recent years; The silicon tetrachloride as by-product of polysilicon aftertreatment mainly contains three kinds of methods: the one, and hydro-reduction is produced the trichlorosilane method; Though this method can be recycled a part of silicon tetrachloride, should technology also exist problems such as the trichlorosilane yield is low, production cost is high, the big height of project investment at present; The 2nd, utilize the thermal silica of silicon tetrachloride production high added value.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, adopts the silicon tetrachloride that the thermal silica technology can't be a large amount of merely; The 3rd, the Direct Water solution generates Hydrogen chloride and silicon-dioxide.Chinese invention patent CN101591018A proposes silicon tetrachloride and Hydrogen chloride and fresh water to be reacted generation hydrogen chloride gas and silicon-dioxide in reactor drum.A certain amount of silicon tetrachloride of this art breading needs a large amount of water or Hydrogen chloride, and the hydrogen chloride gas that generates needs to resolve behind the hydrochloric acid enrichment again and obtain, so this technological process is comparatively complicated.
Summary of the invention
The present invention is directed to shortcoming of the prior art a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride is provided, this method technological process is simple, and cost is low, is convenient to produce implement.
The present invention is achieved through following technical scheme:
A kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride of the present invention, it may further comprise the steps:
Additive and tensio-active agent joined contain in the closed reactor of aqueous hydrochloric acid that mass concentration is 5%-30%, in closed reactor, add silicon tetrachloride then again, said silicon tetrachloride feeding amount is controlled at 0.4-0.9m
3/ h, the controlled temperature reaction that under 20-50 ℃, is hydrolyzed generates silicon sol and hydrogen chloride gas, and said hydrogen chloride gas is recycled after drying.
Said silicon sol filters said precipitation of silica, wash and remove residual additive through still aging formation precipitation of silica; Silicon dioxide colloid after the washing obtains precipitated silica (silicon-dioxide) after drying.
Described additive negatively charged ion is one or both in the inorganic salt that constitute of sulfate radical and/or cl ions, and described additive positively charged ion is one or both in the inorganic salt that constitute of sodium ion, mg ion, calcium ion and/or ammonium ion.
The amount of said additive is the 3-20% of reactant gross weight.
Described tensio-active agent is a kind of among sodium lauryl sulphate, X 2073 or the OP-10 (TX10).
The amount of said tensio-active agent is the 2-5% of reactant gross weight.
The amount of said silicon tetrachloride is reactant gross weight 5-35%.
Preferably, described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, it is further comprising the steps of: the water that washs is mixed with additive solution recycles.
Preferably, described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, it is further comprising the steps of: the hydrogen chloride gas that described reaction generates reclaims and is used to produce trichlorosilane or PVC.
Preferably, described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, the amount of said additive is the 10-15% of reactant gross weight.
Preferably, described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, the amount of said tensio-active agent is the 3-4% of reactant gross weight.
Preferably, described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, the amount of said silicon tetrachloride are reactant gross weight 15-20%.
Preferably, described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, it is further comprising the steps of:
Adding 50L mass concentration is 28% hydrochloric acid soln in closed reactor; The mixture that adds 8kg additive magnesium chloride and ammonium chloride again, wherein magnesium chloride and ammonium chloride respectively account for 4kg, add 2kg tensio-active agent OP-10 again; In chuck, feeding steam after stirring again heats; Control reaction temperature slowly joins silicon tetrachloride in the closed reactor at 45 ℃ then, and the flow of control silicon tetrachloride is at 0.5m
3/ h, the amount control still internal reaction liquid temp through the adjustment recirculated cooling water in the adition process is 45-50 ℃, the hydrogen chloride gas that produces in the reaction is sent to the trichlorosilane production equipment after dust removal by filtration, drying.After silicon tetrachloride reaction finishes, separate and wash draining into straining installation behind the feed liquid ageing 1h, mother liquor water is delivered to mother liquor holding tank, and washing water are sent into the lean solution storage tank as the mother liquor make up water, and the solid after the washing obtains precipitated silica through granulation, drying.
The present invention compares with existing silicon tetrachloride technology for hydrolyzing, has the following advantages:
1. the gelation process of additive and tensio-active agent control colloidal sol has slackened the generation that silica dioxide granule is reunited, and increases the flowability of reaction solution, widens action pane, improves operability.
2. simultaneously the inventive method is utilized in the reaction solution salt effect of additive that hydrogen chloride gas is directly resolved under the lower condition of acid concentration to obtain.Reduce in the traditional water solution hydrogen chloride gas and resolved this complicated technology link again after through the hydrochloric acid enrichment, simplified technical process.
3. technical process is simple, and raw material is easy to get, and scale of investment is little, and cost is low, is convenient to produce implement.
Embodiment
Through specific embodiment the present invention is further described below:
Embodiment 1
Adding 80L mass concentration is 20% hydrochloric acid soln in closed reactor, adds 10kg additive magnesium chloride, and 3kg tensio-active agent X 2073 feeds steam again and heats in chuck after stirring, and control reaction temperature is at 35 ℃.Silicon tetrachloride is slowly joined in the reaction kettle, and the flow of control silicon tetrachloride is at 0.6m
3/ h, the amount control still internal reaction liquid temp through the adjustment recirculated cooling water in the adition process is 35-42 ℃.Be sent to the trichlorosilane process units after the hydrogen chloride gas that produces in reaction dedusting after filtration, the drying.After silicon tetrachloride reaction finishes, separate and wash draining into straining installation behind the feed liquid ageing 1h, mother liquor water is delivered to mother liquor holding tank, and washing water are sent into the lean solution storage tank as the mother liquor make up water, and the solid after the washing obtains precipitated silica through granulation, drying.
Embodiment 2
Adding 50L mass concentration is 28% hydrochloric acid soln in closed reactor; Add 8kg additive magnesium chloride and ammonium chloride mixt; Wherein magnesium chloride and ammonium chloride respectively account for 4kg; 2kg tensio-active agent OP-10 feeds steam again and heats in chuck after stirring, control reaction temperature is at 45 ℃.Silicon tetrachloride is slowly joined in the reaction kettle, and the flow of control silicon tetrachloride is at 0.5m
3/ h, the amount control still internal reaction liquid temp through the adjustment recirculated cooling water in the adition process is 45-50 ℃.Be sent to the trichlorosilane process units after the hydrogen chloride gas that produces in reaction dedusting after filtration, the drying.After silicon tetrachloride reaction finishes, separate and wash draining into straining installation behind the feed liquid ageing 1h, mother liquor water is delivered to mother liquor holding tank, and washing water are sent into the lean solution storage tank as the mother liquor make up water, and the solid after the washing obtains precipitated silica through granulation, drying.
Embodiment 3
Adding 60L mass concentration is 18% hydrochloric acid soln in closed reactor, adds additive ammonium chloride 4kg, calcium chloride 6kg; Tensio-active agent X 2073 2.5kg feeds steam again and heats in chuck after stirring, control reaction temperature is at 25 ℃.Silicon tetrachloride is slowly joined in the reaction kettle, and the flow of control silicon tetrachloride is at 0.6m
3/ h, the amount control still internal reaction liquid temp through the adjustment recirculated cooling water in the adition process is 25-32 ℃.Be sent to the trichlorosilane process units after the hydrogen chloride gas that produces in reaction dedusting after filtration, the drying.After silicon tetrachloride reaction finishes, separate and wash draining into straining installation behind the feed liquid ageing 1h, mother liquor water is delivered to mother liquor holding tank, and washing water are sent into the lean solution storage tank as the mother liquor make up water, and the solid after the washing obtains precipitated silica through granulation, drying.
Embodiment 4
Adding 60L mass concentration is 15% hydrochloric acid soln in closed reactor, adds additive sulfuric acid sodium 6kg, calcium chloride 5kg; Tensio-active agent sodium lauryl sulphate 2.6kg feeds steam again and heats in chuck after stirring, control reaction temperature is at 25 ℃.Silicon tetrachloride is slowly joined in the reaction kettle, and the flow of control silicon tetrachloride is at 0.6m
3/ h, the amount control still internal reaction liquid temp through the adjustment recirculated cooling water in the adition process is 25-32 ℃.Be sent to the trichlorosilane process units after the hydrogen chloride gas that produces in reaction dedusting after filtration, the drying.After silicon tetrachloride reaction finishes, separate and wash draining into straining installation behind the feed liquid ageing 1h, mother liquor water is delivered to mother liquor holding tank, and washing water are sent into the lean solution storage tank as the mother liquor make up water, and the solid after the washing obtains precipitated silica through granulation, drying.
Below table one be the precipitated silica product that obtains of the foregoing description and the comparative result of industry standard HG/T3061-1999.
Table one
| Project | The industry standard index | Embodiment 1 data | Embodiment 2 data |
| Dioxide-containing silica, % >;= | 90 | 92.8 | 93.2 |
| Color | Be superior to, equal standard specimen | Qualified | Qualified |
| Screenings (45 μ m) %<= | 0.5 | 0.45 | 0.39 |
| Weight loss on heating, % | 4.0～8.0 | 5.8 | 7.2 |
| Burning decrement, %<= | 7.0 | 4.8 | 6.1 |
| The pH value | 5.0～8.0 | 6.3 | 5.9 |
| The DBP absorption value, cm 3/g | 2.0～3.5 | 2.7 | 2.6 |
| Tensile strength, Mpa >;= | 17.0 | 18 | 17.5 |
| Tensile yield, % >;= | 675 | 705 | 688 |
| 500% stress at definite elongation, Mpa >;= | 6.3 | 6.4 | 6.8 |
| Total copper content, mg/kg<= | 30 | 19 | 22 |
| Total manganese content, mg/kg<= | 50 | 18 | 15 |
| Total iron content, mg/kg<= | 1000 | 336 | 380 |
Claims (7)
1. method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride is characterized in that it may further comprise the steps:
Additive and tensio-active agent joined contain in the closed reactor of aqueous hydrochloric acid that mass concentration is 5%-30%, in closed reactor, add silicon tetrachloride then again, said silicon tetrachloride feeding amount is controlled at 0.4-0.9m
3/ h, the controlled temperature reaction that under 20-50 ℃, is hydrolyzed generates silicon sol and hydrogen chloride gas, and said hydrogen chloride gas is recycled after drying;
Said silicon sol filters said precipitation of silica, wash and remove residual additive through still aging formation precipitation of silica; Silicon dioxide colloid after the washing obtains precipitated silica (silicon-dioxide) after drying;
Described additive negatively charged ion is one or both in the inorganic salt that constitute of sulfate radical and/or cl ions, and described additive positively charged ion is one or both in the inorganic salt that constitute of sodium ion, mg ion, calcium ion and/or ammonium ion;
The amount of said additive is the 3-20% of reactant gross weight;
Described tensio-active agent is a kind of among sodium lauryl sulphate, X 2073 or the OP-10 (TX10);
The amount of said tensio-active agent is the 2-5% of reactant gross weight;
The amount of said silicon tetrachloride is reactant gross weight 5-35%.
2. like claims 1 described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, it is characterized in that it is further comprising the steps of:
The water that washs is mixed with additive solution to be recycled.
3. like claims 1 described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, it is characterized in that it is further comprising the steps of:
The hydrogen chloride gas that described reaction generates reclaims and is used to produce trichlorosilane or PVC.
4. like claims 1 described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, it is characterized in that:
The amount of said additive is the 10-15% of reactant gross weight.
5. like claims 1 described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, it is characterized in that:
The amount of said tensio-active agent is the 3-4% of reactant gross weight.
6. like claims 1 described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, it is characterized in that:
The amount of said silicon tetrachloride is reactant gross weight 15-20%.
7. like claims 1 described a kind of method of utilizing the silicon tetrachloride as by-product of polysilicon hydrolysis to prepare silicon-dioxide and hydrogenchloride, it is characterized in that it is further comprising the steps of:
Adding 50L mass concentration is 28% hydrochloric acid soln in closed reactor; The mixture that adds 8kg additive magnesium chloride and ammonium chloride again, wherein magnesium chloride and ammonium chloride respectively account for 4kg, add 2kg tensio-active agent OP-10 again; In chuck, feeding steam after stirring again heats; Control reaction temperature slowly joins silicon tetrachloride in the closed reactor at 45 ℃ then, and the flow of control silicon tetrachloride is at 0.5m
3/ h, the amount control still internal reaction liquid temp through the adjustment recirculated cooling water in the adition process is 45-50 ℃, the hydrogen chloride gas that produces in the reaction is sent to the trichlorosilane production equipment after dust removal by filtration, drying.After silicon tetrachloride reaction finishes, separate and wash draining into straining installation behind the feed liquid ageing 1h, mother liquor water is delivered to mother liquor holding tank, and washing water are sent into the lean solution storage tank as the mother liquor make up water, and the solid after the washing obtains precipitated silica through granulation, drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044790A (en) * | 2016-05-31 | 2016-10-26 | 安徽省含山县锦华氧化锌厂 | Method for preparing white carbon black with precipitation method |
| CN106395833A (en) * | 2016-08-31 | 2017-02-15 | 湖北金伟新材料有限公司 | Preparation method for preparing silica sol for catalyst high in purity and uniform in particle size |
| CN115180628A (en) * | 2022-06-27 | 2022-10-14 | 中琦(广东)硅材料股份有限公司 | Processing method of high-purity silicon dioxide powder |
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| CN101591018A (en) * | 2008-05-30 | 2009-12-02 | 中蓝晨光化工研究院有限公司 | The recoverying and utilizing method of silicon tetrachloride in the production process of trichlorosilane |
| CN101734667A (en) * | 2009-12-23 | 2010-06-16 | 昊华宇航化工有限责任公司 | Process for producing precipitated white carbon black by silicon tetrachloride |
| CN101823718A (en) * | 2010-05-07 | 2010-09-08 | 李平 | Method for producing silica by hydrolyzing and precipitating silicon tetrachloride at low temperature |
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2012
- 2012-01-09 CN CN2012100052577A patent/CN102583397A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101591018A (en) * | 2008-05-30 | 2009-12-02 | 中蓝晨光化工研究院有限公司 | The recoverying and utilizing method of silicon tetrachloride in the production process of trichlorosilane |
| CN101734667A (en) * | 2009-12-23 | 2010-06-16 | 昊华宇航化工有限责任公司 | Process for producing precipitated white carbon black by silicon tetrachloride |
| CN101823718A (en) * | 2010-05-07 | 2010-09-08 | 李平 | Method for producing silica by hydrolyzing and precipitating silicon tetrachloride at low temperature |
Non-Patent Citations (1)
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| 吴明明等: "利用四氯化硅制备二氧化硅粉体的研究", 《包装学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044790A (en) * | 2016-05-31 | 2016-10-26 | 安徽省含山县锦华氧化锌厂 | Method for preparing white carbon black with precipitation method |
| CN106044790B (en) * | 2016-05-31 | 2018-01-09 | 安徽省含山县锦华氧化锌厂 | A kind of method of preparing white carbon black by precipitation method |
| CN106395833A (en) * | 2016-08-31 | 2017-02-15 | 湖北金伟新材料有限公司 | Preparation method for preparing silica sol for catalyst high in purity and uniform in particle size |
| CN115180628A (en) * | 2022-06-27 | 2022-10-14 | 中琦(广东)硅材料股份有限公司 | Processing method of high-purity silicon dioxide powder |
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Application publication date: 20120718 |