CN101829665A - Treatment method of byproduct sulfate in process of producing solar grade polysilicon through silane method - Google Patents
Treatment method of byproduct sulfate in process of producing solar grade polysilicon through silane method Download PDFInfo
- Publication number
- CN101829665A CN101829665A CN200910119208A CN200910119208A CN101829665A CN 101829665 A CN101829665 A CN 101829665A CN 200910119208 A CN200910119208 A CN 200910119208A CN 200910119208 A CN200910119208 A CN 200910119208A CN 101829665 A CN101829665 A CN 101829665A
- Authority
- CN
- China
- Prior art keywords
- sulfate
- sodium
- byproduct
- aluminum
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a treatment method of a byproduct sulfate in the process of producing solar grade polysilicon through the silane method. The method comprises the following steps: adding acid substances (such as sulfuric acid, hydrochloric acid and the like) or alkaline substances (such as sodium hydroxide, sodium carbonate, sodium bicarbonate, calcium oxide, calcium hydroxide and the like) in the byproduct sulfate mixture according to the pH value of the mixture, to obtain mixed materials which mainly contain sodium aluminum sulfate, and drying the materials, to obtain a product with the purity of the sodium aluminum sulfate of more than 80%; and the method can also carry out low-temperature crystallization or alkaline chemical precipitation on water solution of the byproduct sulfate mixture, thereby respectively obtaining anhydrous sodium sulfate, sodium sulfate decahydrate, anhydrous aluminum sulphate (glauber salt), crystalline aluminum sulfate, polymer aluminum sulfate, aluminum hydroxide and other products, and solving the problem of utilizing solid wastes produced in the polysilicon production process.
Description
Technical field
The present invention relates to silane thermal decomposition process and produce the processing method of byproduct sulfate in the solar-grade polysilicon technology, wherein in the byproduct sulfate mixture, pH value according to mixture, add acid (as sulfuric acid, hydrochloric acid etc.) or alkalescence (as NaOH, sodium carbonate, sodium acid carbonate, calcium oxide, calcium hydroxide etc.) material, obtain the mixed material based on aluminum sodium sulfate of pH value in the 0-9 scope, with drying materials just aluminum sodium sulfate purity greater than 80% product.The byproduct sulfate mixture also can treatedly obtain anhydrous sodium sulfate, sal glauberi, anhydrous slufuric acid aluminium (glauber salt), products such as crystalline sulfuric acid aluminium, polyaluminium sulfate, aluminium hydroxide respectively.
Background technology
New silane decomposition is divided into two kinds, a kind of silane (SiH that decomposes on fluid bed
4) obtaining granular polycrystalline silicon, another kind is to use
SiH
4Be raw material growing silicon polycrystal crystal rod in the minor siliceous deposits stove of west door.Fluidized bed process is produced granular polycrystalline silicon, produces NaAlH by hydrogenation earlier
4And utilize H
2SiF
6Decompose and make SiF
4, with NaAlH
4Reduction SiF
4Make thick silane, thick silane through be purified to purity 99.9999% or more after with liquid form storage basin in.Very little seed particles at first is imported in the fluidized-bed reactor, feeds silane and hydrogen by a certain percentage, and silane carries out pyrolysis on fluid bed.Carry out around the seed crystal of thermal decomposition of silane on fluid bed, seed particles is grown up gradually, till length arrives about average-size 1mm.
Liquid Si F
4Can also decompose and grow rod-like polycrystal silicon in the minor siliceous deposits stove of west door, the hydrogen that reaction produces then returns hydrogenation process.Its advantage is a polysilicon product purity height, is applicable to growing by zone melting high resistant monocrystalline silicon, and the silane rates of decomposing and transforming is up to 99%, and accessory substance is few, and shortcoming is that the microfine silica soot is more.
No matter the byproduct sulfate mixture which kind of method produced all exists in a large number, reasonably processing method is most important for integrated artistic.We adopt following several method to handle mixture, obtain different product aluminum sodium sulfate, anhydrous sodium sulfate, sal glauberi, anhydrous slufuric acid aluminium (glauber salt), crystalline sulfuric acid aluminium, polyaluminium sulfate, aluminium hydroxide etc.Solve the solid waste that is produced in the production of polysilicon technology and utilized problem.
Summary of the invention
The object of the present invention is to provide and handle the byproduct sulfate waste material that new silane thermal decomposition process polysilicon process produces, according to material properties difference, produce aluminum sodium sulfate, anhydrous sodium sulfate, sal glauberi, anhydrous slufuric acid aluminium (glauber salt), products such as crystalline sulfuric acid aluminium, polyaluminium sulfate, aluminium hydroxide respectively according to ternary alkali phasor.
The present invention realizes by following measure:
(1), directly the method for double salt generation is produced anhydrous slufuric acid aluminium sodium
In reactor, add byproduct mixed sulfate material, Acidity of Aikalinity according to material, for acid material, the aqueous solution (weight concentration is 0.5%～70%) that adds alkali (as NaOH, sodium carbonate, sodium acid carbonate etc.) is removed the sulfuric acid in the mixture, partially fluorinated aluminium makes two sulfate be converted into double salt; For alkaline material, add the Acidity of Aikalinity that mixed material is regulated in acid (as sulfuric acid, hydrochloric acid, carbonic acid etc.), obtain the mixed material based on aluminum sodium sulfate of pH value in the 0-9 scope.Then with the gained drying materials, just aluminum sodium sulfate purity greater than 80% dehydrating prods;
(2), aqueous solution separation method:
With byproduct sulfate water-soluble (in the concentration range 4%～62% of sulfate radical),, get sal glauberi in crystallisation by cooling below 5 ℃.Ten water sulfate evaporative crystallization are again produced anhydrous sodium sulfate (glauber salt) as a product.
The mother liquor condensing crystallizing can get aluminum sulfate or add alkali and get the polyaluminum sulfate aluminum solutions.
(3) add alkali treatment method
With byproduct sulfate mixture water-soluble (weight percent concentration is 1%～80%), add alkaline matter (as NaOH, sodium carbonate, sodium acid carbonate etc.) precipitated aluminium hydroxide, through ageing, sedimentation, Separation of Solid and Liquid, in the dry aluminium hydroxide product that obtains.The residue mother liquor divides two methods to handle:
1, concentrated mother liquor gets anhydrous sodium sulfate (glauber salt);
2, mixed liquor gets sal glauberi in crystallization below 5 ℃, produces anhydrous sodium sulfate through filtration, evaporative crystallization then
The specific embodiment
Enumerate 14 embodiment below, the present invention is further specified, but the present invention is not only limited to these embodiment.
The present invention utilizes three kinds of methods that the target material is handled respectively and obtains different other industrial chemicals that actual use is arranged, material for water treatment etc. with the physical property and the chemical property difference of system.
Embodiment 1: directly double salt generates
(weight of material consists of Na to add byproduct mixed sulfate 100.0g in reactor
+, 8.7%; Al
3+, 10.8%; SO
4 2-, 74.6%; F
-, 0.1%; H
+, 0.11%; Residue is other impurity), add sodium hydroxide solution (weight concentration is 1.0%) 40.0Kg through preheating, fully to react 4 hours, its pH value is 6.5.Oven dry obtains the thick product 103.0g of aluminum sodium sulfate.Change brilliant, the dry 100.5g aluminum sodium sulfate product that gets through ageing again.
Embodiment 2: directly double salt generates
(weight of material consists of Na to add byproduct mixed sulfate material 100.0g in reactor
+, 4.5%; Al
3+, 9.5%; SO
4 2-, 60.5%; F
-, 5.0%; H
+, 1.0%; Residue is other impurity), add sodium hydroxide solution (weight concentration is 18%) 38.9g through preheating, fully to react 2 hours, its pH value is 9.0.Oven dry obtains the thick product 107g of aluminum sodium sulfate.Change brilliant, the dry 102.7g aluminum sodium sulfate product that gets through ageing again.
Embodiment 3: directly double salt generates
(weight of material consists of Na to add byproduct mixed sulfate material 100.0g in reactor
+, 8.28%; Al
3+, 10.3%; SO
4 2-, 76.6%; F
-, 2.45%; H
+, 2.21%); Add sodium hydroxide solution (weight concentration the is 70%) 65.0g through being preheating to, add alumina powder 102.0g, fully reacted 4 hours, its pH value is 0.0.Obtain the thick product 246.6g of aluminum sodium sulfate.Change brilliant, the dry 240.0g aluminum sodium sulfate product that gets through ageing again.
Embodiment 4: the direct double salt of alkaline material generates
(weight of material consists of Na to add byproduct mixed sulfate material 100.0Kg in reactor
+, 9.18%; Al
3+, 11.2%; SO
4 2-, 76.6%; F
-, 2.45%; H
+, 0%; Residue is other impurity); Add sulfuric acid solution (concentration is 10%) 2.3g, fully reacted 6 hours through preheating.Obtain the thick product 100.5g of aluminum sodium sulfate, change brilliant, the dry 99.2g aluminum sodium sulfate product that gets through ageing again.
Embodiment 5: sal glauberi separates
(weight of material consists of Na to get byproduct mixed sulfate material 100.0g
+, 20.18%; Al
3+, 3.9%; 8O
4 2-, 72.6%; F
-, 2.45%; H
+, 1.01%; Residue is other impurity); Be dissolved in the 2000g water, be cooled to 5 ℃ of following thermostatical crystallizations 3 hours, filter, get sal glauberi 4.5g.
Embodiment 6: sal glauberi separates
(weight of material consists of Na to get byproduct mixed sulfate material 100.0g
+, 20.18%; Al
3+, 3.9%; 8O
4 2-, 72.6%; F
-, 2.45%; H
+, 1.01%; Residue is other impurity), be dissolved in the 240g water, be cooled to 0 ℃ of following thermostatical crystallization 3 hours, filter, get sal glauberi 220g.
Embodiment 7: sal glauberi separates
(weight of material consists of Na to get byproduct mixed sulfate material 100.0g
+, 8.7%; Al
3+, 10.8%; SO
4 2-, 74.6%; F
-, 0.1%; H
+, 0.11%; Residue is other impurity); Be dissolved in the 240g water, be cooled to 0 ℃ of following thermostatical crystallization 3 hours, filter, get sal glauberi 117.5g.
Embodiment 8: sal glauberi separates
(weight of material consists of Na to get byproduct mixed sulfate material 100.0g
+, 6.5%; Al
3+, 15.5%; SO
4 2-, 74.6%; F
-, 2.25%; H
+, 1.01%; Residue is other impurity; ); Be dissolved in the 120g water, be cooled to 0 ℃ of following thermostatical crystallization 3 hours, filter, get sal glauberi 90.1g.
The crystallization of 9: six water aluminum sulfate of embodiment
Get filtrate mixed liquor 220.0g in the example 7, heating is concentrated into 120.0g, and crystallisation by cooling 4 hours filters, and washing obtains six water aluminum sulfate 88.5g.
Embodiment 10: the polyaluminum sulfate crystalline aluminophosphate
Get filtrate mixed liquor 220.0g in the example 7, add 20% sodium hydrate aqueous solution 148.0g gradually in 80 ℃, obtain salic 7.8% polyaluminum sulfate aluminum solutions 365.5g.
Embodiment 11: anhydrous sodium sulfate (glauber salt) crystallization
Example 6 gained 220.0g sal glauberis are made 45 ℃ of saturated solutions, and heating evaporation moisture content 100g filters while hot, washs, drying, obtains anhydrous sodium sulfate (glauber salt) 93.5g.
Embodiment 12: preparation of aluminium hydroxide
(material is formed Na to get byproduct mixed sulfate material 100.0g
+, 8.72%; Al
3+, 10.8%; SO
4 2-, 74.6%; F
-, 2.45%; H
+, 0.11%; Residue is other impurity) be dissolved in the 240g water, in 4 hours, add 30% sodium hydrate aqueous solution 25.0g then, precipitated aluminium hydroxide, through ageing, sedimentation, Separation of Solid and Liquid, drying obtains aluminium hydroxide product 28.2g.
Embodiment 13: preparation of aluminium hydroxide
(weight of material consists of Na to get byproduct mixed sulfate material 100.0g
+, 8.72%; Al
3+, 10.8%; SO
4 2-, 74.6%; F
-, 2.45%; H
+, 0.11%; Residue is other impurity; ) be dissolved in the 2000g water, in 3 hours, add 20% sodium hydrate aqueous solution 25.0g then.Through ageing, sedimentation, Separation of Solid and Liquid, drying obtains aluminium hydroxide product 29g.
Embodiment 14: preparation of aluminium hydroxide
(weight of material consists of Na to get byproduct mixed sulfate material 100.0g
+, 6.5%; Al
3+, 15.5%; SO
4 2-, 74.6%; F
-, 2.25%; H
+, 1.01%; Residue is other impurity) be dissolved in the 120g water, in 3 hours, add 30% sodium hydrate aqueous solution 25.0g then.Through ageing, sedimentation, Separation of Solid and Liquid, drying obtains aluminium hydroxide product 43.8g.
Claims (4)
1. silane thermal decomposition process is produced the processing method of byproduct sulfate in the solar-grade polysilicon technology.
2. according to claim 1, processing method is meant in the sulfate mixture of byproduct, pH value according to mixture, add acid (as sulfuric acid, hydrochloric acid etc.) or alkalescence (as NaOH, sodium carbonate, sodium acid carbonate, calcium oxide, calcium hydroxide etc.) material, obtain the mixed material based on aluminum sodium sulfate of pH value in the 0-9 scope, with drying materials just aluminum sodium sulfate purity greater than 80% product.
3. according to claim 1, can also the byproduct sulfate mixture is water-soluble (in the concentration range 4%～62% of sulfate radical), in crystallisation by cooling below 5 ℃, sal glauberi.Ten water sulfate evaporative crystallization are again produced anhydrous sodium sulfate (glauber salt) as a product.The mother liquor condensing crystallizing can get aluminum sulfate or add alkali and get the polyaluminum sulfate aluminum solutions.
4. according to claim 1, with sulfate mixture water-soluble (weight percent concentration is 1%～80%), add alkaline matter (as NaOH, sodium carbonate, sodium acid carbonate etc.) precipitated aluminium hydroxide, through ageing, sedimentation, Separation of Solid and Liquid, drying obtains the aluminium hydroxide product.The residue mother liquor divides two methods to handle:
A) concentrated mother liquor gets anhydrous sodium sulfate (glauber salt);
B) mixed liquor gets sal glauberi in crystallization below 5 ℃, produces anhydrous sodium sulfate through filtration, evaporative crystallization then.
5 according to claim 1, and this method is applicable to material handling composition (weight fraction):
Na
+ 4.5％～20.1％； Al
3+ 3.9％～15.5％
SiO
2 0％～4％； F
- 0～5％
H
+ 0～6％； SO
4 2- 32％～89.6％
Other impurity 0～20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910119208A CN101829665A (en) | 2009-03-09 | 2009-03-09 | Treatment method of byproduct sulfate in process of producing solar grade polysilicon through silane method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910119208A CN101829665A (en) | 2009-03-09 | 2009-03-09 | Treatment method of byproduct sulfate in process of producing solar grade polysilicon through silane method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101829665A true CN101829665A (en) | 2010-09-15 |
Family
ID=42713963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910119208A Pending CN101829665A (en) | 2009-03-09 | 2009-03-09 | Treatment method of byproduct sulfate in process of producing solar grade polysilicon through silane method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101829665A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491339A (en) * | 2011-12-19 | 2012-06-13 | 天津市泰源工业气体有限公司 | Method for preparing silane from sodium aluminum hydride and silicon tetrafluoride |
-
2009
- 2009-03-09 CN CN200910119208A patent/CN101829665A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491339A (en) * | 2011-12-19 | 2012-06-13 | 天津市泰源工业气体有限公司 | Method for preparing silane from sodium aluminum hydride and silicon tetrafluoride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100410174C (en) | Method for preparing aluminum oxide | |
| WO2018113478A1 (en) | Method for producing lithium hydroxide monohydrate using lithium carbonate as raw material | |
| CN108238621B (en) | Method for producing polyaluminum chloride by using by-product of diethyl methylphosphonite production | |
| KR20170088873A (en) | Production of Lithium Hydroxide | |
| CN101891165A (en) | Production method of macrocrystalline hexagonal boron nitride | |
| CN102320585B (en) | Method for direct production of industrial-grade ammonium biphosphate by wet-process phosphoric acid | |
| CN108996526B (en) | Preparation method of large-particle heavy sodium bicarbonate | |
| CN101624198A (en) | Method for preparing basic magnesium chloride and magnesium oxide by pyrolyzing bischofite | |
| CN104876253A (en) | Method for treating calcium in high-calcium fly ash | |
| CN109516628A (en) | A method of extracting magnesium sulfate from high magnesium low calcium power plant effluent | |
| CN103936034B (en) | Preparation method of high-purity sodium iodide powder | |
| JP4516023B2 (en) | How to recover potassium sulfate | |
| CN106379913A (en) | Method for synthesizing P zeolite molecular sieve from rice husk | |
| CN103121699A (en) | Method for preparing potassium fluoride by utilizing potassium fluosilicate | |
| WO2012079274A1 (en) | Process for producing polycrystal silicon using sodium fluorosilicate as by-product of phosphate fertilizer industry | |
| JPH0249247B2 (en) | ||
| CN1174921C (en) | High-purity mangesium oxide or magnesium carbonate preparing process in circular medium | |
| CA2234650C (en) | Method for producing calcium borate | |
| CN107162935A (en) | The recovery method of phosphorus-containing compound in useless chemical polishing agent | |
| CN1234596C (en) | Process for preparing fluorine compound and SiO2 from sodium fluosilicate | |
| CN101829665A (en) | Treatment method of byproduct sulfate in process of producing solar grade polysilicon through silane method | |
| CN107720767B (en) | Method for hydrothermally synthesizing kaolinite from anorthite | |
| CN107601536B (en) | Method for extracting aluminum oxide from high-alumina fly ash | |
| CN101319382B (en) | Calcium sulphate crystal whisker preparation method with sea water bittern as raw material | |
| CN105329974B (en) | A kind of method that fluorine is reclaimed from fluoride waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100915 |