CN1760124A - Method for reactivating and regenerating waste silicon powder - Google Patents
Method for reactivating and regenerating waste silicon powder Download PDFInfo
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- CN1760124A CN1760124A CN 200510045072 CN200510045072A CN1760124A CN 1760124 A CN1760124 A CN 1760124A CN 200510045072 CN200510045072 CN 200510045072 CN 200510045072 A CN200510045072 A CN 200510045072A CN 1760124 A CN1760124 A CN 1760124A
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Abstract
A process for regenerating used silicon powder includes such steps as washing with organic solvent for removing the organic pollutant from its surface, adding sulfuric acid, removing metallic oxides by reactive dissolving, adding nitric acid as catalyst, washing with sulfuric acid, reacting while stirring for removing Cu, separating solid to obtain regenerated silicon powder, water washing and drying in the air.
Description
(1) technical field
The present invention relates to a kind of method for reactivating and regenerating waste silicon powder, belong to resource and technical field of environmental science.
(2) background technology
Organosilicon material has fabulous high-low temperature resistant, anti-ozone, ageing-resistant performance, and physiology inertia and weathering resistance ideal become the critical material in new high-tech material field, national defense industry and other many fields, are described as the monosodium glutamate of modern industry.Recent two decades comes, and organosilicon industry obtains high speed development.According to incompletely statistics, only the global ultimate production of methyl chlorosilane just up to 1800kt/.
Pure Silicon Metal is the basic material of synthesizing organosilicon monomer, and consumption enlarges year by year.Present domestic annual consumption surpasses 100,000 tons, and the annual demand in world market China silica flour quantity is about 3～40,000 tons, and every year is with about 20% speed increase.Pure Silicon Metal is mainly derived from the natural product electromachining at present.Be subjected to the restriction of the resource and the energy, price is in continuous rising, and profit significantly reduces, and needs the new source of exploitation.
In the organosilane monomer production process, mainly be catalyzer with copper, usage quantity is about the 2-10% of silica flour total amount, during use and silica flour mix reaction.Because of reason such as floating, sedimentation and reaction be incomplete, produce a large amount of waste silicon powders, quantity accounts for 8～10% of the total input amount of silica flour.Will generate up to ten thousand tons of waste silicon powders every year.This part silica flour is because of poisoning loses reactive behavior, granular size is inhomogeneous, surperficial by Organic pollutants, and wherein the maximum impurity of amount is metallic copper and cupric oxide, and quantity is about 10% of useless silicon total amount, also contains a spot of Fe in addition
2O
3With ZnO etc.So the waste silicon powder of enormous amount becomes the exhaust emission environment, deposits occupied ground and easily causes the refuse of secondary pollution.How turning waste into wealth, eliminate environmental pollution, is the very important difficult problem that organosilane monomer manufacturer faces, and also becomes the environmental problem that needs to be resolved hurrily.Present domestic organosilane monomer main manufacturer, urgent hope solves this technical barrier.Therefore, waste silicon powder being brought back to life regeneration has important practical significance.
Through looking into new proof:,, do not see relevant report at present as complete method for reactivating and regenerating waste silicon powder relevant for the pertinent literature of organosilicon waste catalyst.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, at the waste silicon powder that produces in the organosilane monomer production process, a kind of method for reactivating and regenerating waste silicon powder is proposed, this method can be brought back to life regeneration with waste silicon powder, produce qualified industrial silica fume, can produce byproduct copper sulfate and metallic copper, have remarkable economic efficiency and environmental benefit.
Method for reactivating and regenerating waste silicon powder of the present invention, step is as follows:
1. under the normal temperature, waste silicon powder is carried out stirring and washing, the organic pollutant on flush away waste silicon powder surface with organic solvent.The consumption of solvent is decided according to the waste silicon powder pollution level, and the cleaning reaction time is 24 hours, and stirring velocity is 30～70 rev/mins.
The above-mentioned organic solvent and the weight ratio of silica flour are generally: organic solvent: waste silicon powder=0.5～1: 1～2.
2. the waste silicon powder with flush away surface organic pollutant places reactor, and adding mass percentage concentration is that 20～30% sulfuric acid are removed dissolvings such as metal oxide cupric oxide, ferric oxide and zinc oxide.In the reaction process, control reaction temperature is 65～70 ℃, insulated and stirred reaction 24 hours, and stirring velocity is 30～70 rev/mins, and oxide compound is reacted completely.Sulfuric acid is reused to PH=1～1.5.The weight ratio of sulfuric acid add-on and waste silicon powder is: sulfuric acid: waste silicon powder=1: 0.8～1.2.Can not be neutralized to PH ≈ 7 dischargings with industrial caustic soda by reusable again spent acid solution.
3. step 2 gained waste silicon powder is placed in the closed reactor, with mass percentage concentration is that 30～50% nitric acid are catalyzer, sulfuric acid scrubbing with mass percentage concentration 50～70%, control reaction temperature is 75～80 ℃, insulated and stirred reaction 24 hours, stirring velocity is 30～70 rev/mins, makes the metallic copper dissolving in the waste silicon powder complete.Contain weight ratio in the waste silicon powder and be 5～18% metallic copper and cupric oxide, the ratio that control adds vitriolic weight and waste silicon powder weight is: sulfuric acid: waste silicon powder=1: 1～1.2.Nitric acid is 1～2% of sulfuric acid weight.Pickle solution is reused some recovery to PH=1～1.5, and the silica flour of solid part for bringing back to life is washed to PH ≈ 7 and dries.The gas backstreaming that produces during reaction is reused.
4. step 3 gained solid part drying and crushing is sieved, be industrial silica fume.Granularity by the GB requirement is packed respectively.
Solid product for step 4 is handled again, continues following steps:
5. with the industrial silica fume and the caustic soda reaction of step 4, make silicon sol.Method is undertaken by the silicon sol production standard.
The processing of the sulphuric acid soln that reclaims for step 3, can continue following steps:
6. the sulphuric acid soln that contains copper sulfate that reclaims in the above-mentioned steps 3 adds purified cupric oxide again, and is complete with remaining sulfuric acid reaction.Cupric nitrate is removed in concentrated, the recrystallization purification of distillation then, gets product copper sulfate.
The another kind of treatment process of the sulphuric acid soln that contains copper sulfate that reclaims for step 3, can continue following steps:
7. adopt redox method, clean iron filings are joined in the sulphuric acid soln that contains copper sulfate of step 3 recovery, metallic copper is cemented out, smelt into copper ingot after the copper powder that displaces dries.The discharging of in the ferrum sulfuricum oxydatum solutum and back.
Organic solvent in the above-mentioned steps 1 is that dehydrated alcohol, industrial ether or industrial ether and dehydrated alcohol were by 1: 1 weight ratio blended mixture.
Method of the present invention is removed silicon powder surface earlier with organic solvent organic pollutant can carry out at normal temperatures.Add sulfuric acid and heat, metal oxide cupric oxide and ferric oxide dissolving are removed, adding with nitric acid is the pickling of heating of the vitriol oil of catalyzer, and with metallic copper oxidation, the dissolving of sneaking in the silica flour, sulphuric acid soln reclaims.Silica flour adopts physical methods such as drying and crushing after the washing neutralization, be processed into qualified industrial silica fume.The sulphuric acid soln that reclaims is used purified cupric oxide earlier, and is complete with remaining sulfuric acid reaction, adopts the method for distilling concentrated and recrystallization then, purified product copper sulfate, and copper sulfate continues deep processing, goes out metallic copper with iron powder replacement.What reaction was discharged mainly is vitriol, very little to the pollution of environment, does not reclaim.
The silica flour of the inventive method preparation, quality reaches the technical indicator of industrial silica fume, can be used for producing organosilicon series product: as silicon sol, organosilicon chlorine monomer, cyclosilane etc.Innovation part of the present invention is to select appropriate organic solvent treat surface pollutent, remove metal oxide cupric oxide and ferric oxide with sulfuric acid, with adding with nitric acid is that the sulfuric acid of catalyzer is heated the method for pickling with the metallic copper oxidation of sneaking in the silica flour, and generation copper sulfate, copper sulfate can continue deep processing, the preparation metallic copper.Both reclaimed the principal constituent silica flour, again major impurity copper had been become the useful industrial product, economic benefit and obvious environment benefit.
(4) embodiment
Embodiment 1:
1. in Sealing Arrangement, be solvent, waste silicon powder is added wherein, clean the organic pollutant of silicon powder surface with the dehydrated alcohol.The cleaning reaction time is 24 hours, and stirring velocity is 30～70 rev/mins.The dehydrated alcohol that adds and the weight ratio of waste silicon powder are: dehydrated alcohol: waste silicon powder=1: 1.
2. the waste silicon powder with flush away surface organic pollutant places reactor, adds mass percentage concentration and is 30% sulfuric acid dissolvings such as metal oxide cupric oxide, ferric oxide and zinc oxide are removed.In the reaction process, control reaction temperature is 65～70 ℃, insulated and stirred reaction 24 hours, and stirring velocity is 30～70 rev/mins, and oxide compound is reacted completely.Sulfuric acid is reused to PH=1～1.5.The weight ratio of sulfuric acid add-on and waste silicon powder is: sulfuric acid: waste silicon powder=1: 1.Can not be neutralized to PH ≈ 7 dischargings with industrial caustic soda by reusable again spent acid solution.
3. step 2 gained waste silicon powder is placed in the closed reactor, with mass percentage concentration is that 40% nitric acid is catalyzer, it with mass percentage concentration 60% sulfuric acid scrubbing, control reaction temperature is 75～80 ℃, insulated and stirred reaction 24 hours, stirring velocity is 30～70 rev/mins, the metallic copper in the dissolving waste silicon powder.The metallic copper and the cupric oxide that contain 5～18% weight ratios in the waste silicon powder, the ratio that control adds vitriolic weight and waste silicon powder is: sulfuric acid: waste silicon powder=1: 1.Nitric acid is 2% of sulfuric acid weight.Pickle solution is reused some recovery to PH=1～1.5, and the silica flour of solid part for bringing back to life is washed to PH ≈ 7 and dries.The gas backstreaming that produces during reaction is reused.
4. the solid part drying and crushing is sieved, form industrial silica fume, pack respectively by the granularity of GB requirement.
Embodiment 2:
1. in Sealing Arrangement, be solvent with industrial ether, clean the organic pollutant of silicon powder surface, this step reaction is stirred at normal temperatures and is carried out.The cleaning reaction time is 24 hours, and stirring velocity is 30～70 rev/mins.The weight ratio of each component is: industrial ether: waste silicon powder=0.8: 1.
2. the waste silicon powder with flush away surface organic pollutant places reactor, and adding mass percentage concentration is that 25% sulfuric acid is removed dissolvings such as metal oxide cupric oxide, ferric oxide and zinc oxide.In the reaction process, control reaction temperature is 65～70 ℃, insulated and stirred reaction 24 hours, and stirring velocity is 30～70 rev/mins, and oxide compound is reacted completely.Sulfuric acid is reused to PH=1～1.5.The weight ratio of sulfuric acid add-on and waste silicon powder is: sulfuric acid: waste silicon powder=1: 0.8.Can not be neutralized to PH ≈ 7 dischargings with industrial caustic soda by reusable again spent acid solution.
3. step 2 gained waste silicon powder is placed in the closed reactor, with mass percentage concentration is that 50% nitric acid is catalyzer, it with mass percentage concentration 70% sulfuric acid scrubbing, control reaction temperature is 75～80 ℃, insulated and stirred reaction 24 hours, stirring velocity is 30～70 rev/mins, the metallic copper in the dissolving waste silicon powder.The metallic copper and the cupric oxide that contain 8～15% weight ratios in the waste silicon powder, the ratio that control adds vitriolic weight and waste silicon powder is: sulfuric acid: waste silicon powder=1: 1.2.Nitric acid is 2% of sulfuric acid weight.Pickle solution is reused some recovery to PH=1～1.5, and the silica flour of solid part for bringing back to life is washed to PH ≈ 7 and dries.The gas backstreaming that produces during reaction is reused.
4. the solid part drying and crushing is sieved, form industrial silica fume, pack respectively by the granularity of GB requirement.
5. the processing of reclaim(ed) sulfuric acid solution: add purified cupric oxide, complete with remaining sulfuric acid reaction.Concentrated, the recrystallization purification of distillation then gets product copper sulfate.
Embodiment 3:
1. in Sealing Arrangement, be solvent with industrial ether and dehydrated alcohol by 1: 1 weight ratio blended mixture, clean the organic pollutant of silicon powder surface, this step reaction is stirred at normal temperatures and is carried out.The cleaning reaction time is 24 hours, and stirring velocity is 30～70 rev/mins.The weight ratio of each component is: industrial ether: dehydrated alcohol: waste silicon powder=0.5: 0.5: 1.2.
2. the waste silicon powder with flush away surface organic pollutant places reactor, and adding mass percentage concentration is that 20% sulfuric acid is removed dissolvings such as metal oxide cupric oxide, ferric oxide and zinc oxide.In the reaction process, control reaction temperature is 65～70 ℃, insulated and stirred reaction 24 hours, and stirring velocity is 30～70 rev/mins, and oxide compound is reacted completely.Sulfuric acid is reused to PH=1～1.5.The weight ratio of sulfuric acid add-on and waste silicon powder is: sulfuric acid: waste silicon powder=1: 0.8.Can not be neutralized to PH ≈ 7 dischargings with industrial caustic soda by reusable again spent acid solution.
3. step 2 gained waste silicon powder is placed in the closed reactor, with mass percentage concentration is that 35% nitric acid is catalyzer, it with mass percentage concentration 55% sulfuric acid scrubbing, control reaction temperature is 75～80 ℃, insulated and stirred reaction 24 hours, stirring velocity is 30～70 rev/mins, the metallic copper in the dissolving waste silicon powder.The metallic copper and the cupric oxide that contain 8～15% weight ratios in the waste silicon powder, the ratio that control adds vitriolic weight and waste silicon powder is: sulfuric acid: waste silicon powder=1: 1.Nitric acid is 2% of sulfuric acid weight.Pickle solution is reused some recovery to PH=1～1.5, and the silica flour of solid part for bringing back to life is washed to PH ≈ 7 and dries.The gas backstreaming that produces during reaction is reused.
4. the solid part drying and crushing is sieved, form industrial silica fume, pack respectively by the granularity of GB requirement.
5. the processing of reclaim(ed) sulfuric acid solution: add purified cupric oxide, complete with remaining sulfuric acid reaction.Concentrated, the recrystallization purification of distillation then gets product copper sulfate.
6. adopt redox method, clean iron filings are joined in the sulphuric acid soln of step 3 recovery, metallic copper is cemented out, smelt into copper ingot after the copper powder that displaces dries.The discharging of in the ferrum sulfuricum oxydatum solutum and back.
Claims (5)
1. a method for reactivating and regenerating waste silicon powder comprises the steps:
(1) under the normal temperature, waste silicon powder is carried out stirring and washing with organic solvent, the organic pollutant on flush away waste silicon powder surface, the cleaning reaction time is 24 hours, stirring velocity is 30～70 rev/mins;
(2) waste silicon powder with flush away surface organic pollutant places reactor, and adding mass percentage concentration is that 20～30% sulfuric acid are removed metal oxide cupric oxide, ferric oxide and zinc oxide dissolving; In the reaction process, control reaction temperature is 65～70 ℃, insulated and stirred reaction 24 hours, and stirring velocity is 30～70 rev/mins, and oxide compound is reacted completely; Sulfuric acid is reused to PH=1～1.5; The weight ratio of sulfuric acid add-on and waste silicon powder is: sulfuric acid: waste silicon powder=1: 0.8～1.2; Can not be neutralized to PH ≈ 7 dischargings with industrial caustic soda by reusable again spent acid solution;
(3) step (2) gained waste silicon powder is placed in the closed reactor, with mass percentage concentration is that 30～50% nitric acid are catalyzer, sulfuric acid scrubbing with mass percentage concentration 50～70%, control reaction temperature is 75～80 ℃, insulated and stirred reaction 24 hours, stirring velocity is 30～70 rev/mins, makes the metallic copper dissolving in the waste silicon powder complete.Contain weight ratio in the waste silicon powder and be 8～15% metallic copper and cupric oxide, the weight ratio that control adds sulfuric acid and waste silicon powder is: sulfuric acid: waste silicon powder=1: 1～1.2; Nitric acid is 1～2% of sulfuric acid weight; Pickle solution is reused some recovery to PH=1～1.5, the silica flour of solid part for bringing back to life, and being washed to PH ≈ 7 dries;
(4) the solid part drying and crushing is sieved, get industrial silica fume.
2. method for reactivating and regenerating waste silicon powder as claimed in claim 1 is characterized in that, the weight ratio of described organic solvent and silica flour is generally: organic solvent: waste silicon powder=0.5～1: 1～2.
3. method for reactivating and regenerating waste silicon powder as claimed in claim 1 is characterized in that, the preferred dehydrated alcohol of described organic solvent, industrial ether or industrial ether and dehydrated alcohol were by 1: 1 weight ratio blended mixture.
4. method for reactivating and regenerating waste silicon powder as claimed in claim 1 is characterized in that, handles for the industrial silica fume of described step (4) again, continues following steps:
(5) with the industrial silica fume and the caustic soda reaction of step (4), make silicon sol.
5. method for reactivating and regenerating waste silicon powder as claimed in claim 1 is characterized in that, the sulphuric acid soln that contains copper sulfate that described step (3) reclaims is (6) or step (7) processing by the following step:
(6) sulphuric acid soln that contains copper sulfate of recovery in the above-mentioned steps (3) adds purified cupric oxide again, and is complete with remaining sulfuric acid reaction, and cupric nitrate is removed in concentrated, the recrystallization purification of distillation then, gets product copper sulfate;
(7) adopt redox method, clean iron filings are joined in the sulphuric acid soln that contains copper sulfate of step (3) recovery, metallic copper is cemented out, smelt into copper ingot after the copper powder that displaces dries, the discharging of in the ferrum sulfuricum oxydatum solutum and back.
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Cited By (9)
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| CN101528597B (en) * | 2006-11-02 | 2011-10-12 | 夏普株式会社 | Silicon reclamation apparatus and method of reclaiming silicon |
| CN102390832A (en) * | 2011-08-18 | 2012-03-28 | 江西赛维Ldk光伏硅科技有限公司 | Method for treating waste silicon powder produced in trichlorosilane synthesis process |
| CN102943177A (en) * | 2012-10-29 | 2013-02-27 | 浙江特力再生资源有限公司 | Method for recovering cooper and silicon powder from organosilicon waste residue |
| CN103395788A (en) * | 2013-07-25 | 2013-11-20 | 江西赛维Ldk太阳能高科技有限公司 | Ingot-casting silicon powder with controllable grain size as well as preparation method and application thereof |
| CN104843721A (en) * | 2015-04-30 | 2015-08-19 | 中国科学院过程工程研究所 | Organic silicon waste contact recovery method |
| CN108249446A (en) * | 2017-12-25 | 2018-07-06 | 河南师范大学 | A kind of method of the cold hydrogenation workshop copper-containing residue integrated application of polysilicon factory |
| CN113716569A (en) * | 2021-10-21 | 2021-11-30 | 长沙岱勒新材料科技股份有限公司 | Method for purifying silicon powder |
| CN114349010A (en) * | 2022-02-23 | 2022-04-15 | 新疆大全绿创环保科技有限公司 | Method for removing carbon from waste silicon powder after copper extraction |
| CN117960254A (en) * | 2024-04-02 | 2024-05-03 | 河南氢力能源有限公司 | Recovery and regeneration process of copper-silicon system spent catalyst in furfural hydrogenation reaction |
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| CN1083418A (en) * | 1992-09-01 | 1994-03-09 | 吴玉琨 | From organic silicon chemical waste residue, reclaim the technology of useful matter |
| NO180188C (en) * | 1994-03-30 | 1997-03-05 | Elkem Materials | Process for the preparation of residues from direct synthesis of organochlorosilanes and / or chlorosilanes |
| DE10017153C1 (en) * | 2000-04-06 | 2001-05-03 | Wacker Chemie Gmbh | Recovery of copper(I) chloride catalyst in direct synthesis of organochlorosilane involves oxidizing copper in process residue in aqueous acid and reducing resultant aqueous copper(II) chloride solution with iron |
| JP3426208B2 (en) * | 2000-11-22 | 2003-07-14 | 三益半導体工業株式会社 | Method of regenerating silicon single crystal wafer with copper film and reclaimed wafer |
| KR20040077038A (en) * | 2003-02-27 | 2004-09-04 | 주식회사 금강고려화학 | The treatment of residual fine particles from direct process manufacture of methylchlorosilane |
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| CN101528597B (en) * | 2006-11-02 | 2011-10-12 | 夏普株式会社 | Silicon reclamation apparatus and method of reclaiming silicon |
| CN102390832A (en) * | 2011-08-18 | 2012-03-28 | 江西赛维Ldk光伏硅科技有限公司 | Method for treating waste silicon powder produced in trichlorosilane synthesis process |
| CN102390832B (en) * | 2011-08-18 | 2013-06-26 | 江西赛维Ldk光伏硅科技有限公司 | Method for treating waste silicon powder produced in trichlorosilane synthesis process |
| CN102943177A (en) * | 2012-10-29 | 2013-02-27 | 浙江特力再生资源有限公司 | Method for recovering cooper and silicon powder from organosilicon waste residue |
| CN103395788A (en) * | 2013-07-25 | 2013-11-20 | 江西赛维Ldk太阳能高科技有限公司 | Ingot-casting silicon powder with controllable grain size as well as preparation method and application thereof |
| CN103395788B (en) * | 2013-07-25 | 2015-05-20 | 江西赛维Ldk太阳能高科技有限公司 | Ingot-casting silicon powder with controllable grain size as well as preparation method and application thereof |
| CN104843721A (en) * | 2015-04-30 | 2015-08-19 | 中国科学院过程工程研究所 | Organic silicon waste contact recovery method |
| CN108249446A (en) * | 2017-12-25 | 2018-07-06 | 河南师范大学 | A kind of method of the cold hydrogenation workshop copper-containing residue integrated application of polysilicon factory |
| CN113716569A (en) * | 2021-10-21 | 2021-11-30 | 长沙岱勒新材料科技股份有限公司 | Method for purifying silicon powder |
| CN114349010A (en) * | 2022-02-23 | 2022-04-15 | 新疆大全绿创环保科技有限公司 | Method for removing carbon from waste silicon powder after copper extraction |
| CN117960254A (en) * | 2024-04-02 | 2024-05-03 | 河南氢力能源有限公司 | Recovery and regeneration process of copper-silicon system spent catalyst in furfural hydrogenation reaction |
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