CN117945405A - Method for preparing high-purity silicon by purifying cut silicon mud - Google Patents
Method for preparing high-purity silicon by purifying cut silicon mud Download PDFInfo
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- CN117945405A CN117945405A CN202311715990.2A CN202311715990A CN117945405A CN 117945405 A CN117945405 A CN 117945405A CN 202311715990 A CN202311715990 A CN 202311715990A CN 117945405 A CN117945405 A CN 117945405A
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- purity silicon
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 92
- 239000010703 silicon Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010306 acid treatment Methods 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 24
- 238000005554 pickling Methods 0.000 claims abstract description 18
- 238000003723 Smelting Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000010891 electric arc Methods 0.000 claims abstract description 11
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000010802 sludge Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims 3
- 238000000746 purification Methods 0.000 abstract description 6
- 238000005520 cutting process Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the technical field of high-purity silicon smelting, and discloses a method for preparing high-purity silicon by using pure cutting silicon mud, which comprises the following steps: (1) Adding the prepared mixed solution into the initial silicon mud for pickling; the mixed solution comprises hydrochloric acid and hydrofluoric acid solution, and a second-stage acid treatment sample is obtained through negative pressure suction filtration; (2) And transferring the obtained two-stage acid treatment sample solid into an electric arc furnace for smelting, impurity removing and purifying to obtain the high-purity silicon. The invention adopts the mixed solution of hydrochloric acid and hydrofluoric acid for two-stage acid treatment smelting, impurity removal and purification to obtain the high-purity silicon with the purity of 99.95 percent. Therefore, the invention can recycle the silicon mud, and the purity of the recycled silicon ingot is higher, thereby greatly promoting the development of producing high-purity silicon by utilizing the recycled silicon mud.
Description
Technical Field
The invention belongs to the technical field of high-purity silicon smelting recovery, and particularly relates to a method for preparing high-purity silicon by purifying cut silicon mud.
Background
Metallic silicon, also known as pure silicon or silicon metal, is a key industrial raw material with a wide range of applications. It is the second most abundant element on earth, next to oxygen, and is widely appreciated due to its excellent physicochemical properties. Metallic silicon is mainly used in semiconductor manufacturing, solar cell, foundry and alloy manufacturing, chemical industry, and the like.
The traditional silicon mud purification method has low efficiency, needs a large amount of chemical reagents and energy sources, simultaneously generates a large amount of waste water and wastes, and increases the production cost and the environmental burden. Some conventional methods may have difficulty in completely removing impurities in the silicon paste, resulting in lower purity of the final product than required, affecting the performance of high-end applications such as semiconductors and solar cells. In addition, conventional silica mud purification methods generally require high energy consumption, including high temperature and high pressure conditions, which increase the energy costs and carbon footprint of the production. Conventional methods may also cause fluctuations in product quality due to difficulty in controlling the content of impurities, which is a serious problem for industries requiring high stability such as semiconductor manufacturing. Therefore, the high energy consumption, chemical reagent and waste treatment cost in the traditional method make the production cost of the silicon mud high, and limit the wide application of the silicon mud.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for preparing high-purity silicon by purifying cut silicon mud, which aims to obtain high-purity silicon and simultaneously realize high optimization of the pretreatment process of the cut silicon mud.
The invention realizes the aim by the following technical proposal:
The invention provides a method for preparing high-purity silicon by purifying cut silicon mud, which comprises the following steps:
(1) Adding the prepared mixed solution into the initial silicon mud for pickling; the mixed solution comprises hydrochloric acid and hydrofluoric acid solution, and a second-stage acid treatment sample is obtained through negative pressure suction filtration;
(2) And transferring the obtained two-stage acid treatment sample solid into an electric arc furnace for smelting, impurity removing and purifying to obtain the high-purity silicon.
Preferably, in the step (1), the volume concentration of the hydrochloric acid is 5-15%.
Preferably, in the step (1), the volume concentration of the hydrofluoric acid solution is 5-15%.
Preferably, step (1) further comprises recovering off-gas generated during the pickling process.
The beneficial effects of the invention are as follows:
The invention provides an innovation of an acid treatment mode of silicon mud, and selection of a selective reagent aims to obtain high-purity silicon and simultaneously realize high optimization of a pretreatment process of cutting silicon mud. The method comprises the steps of firstly treating the silicon mud by two-stage acid to remove organic matters, silicon dioxide and other impurities in the silicon mud, and then smelting, impurity removing and purifying silicon powder by an electric arc furnace to obtain a high-purity compact silicon ingot. Through detection, the purity of the high-purity silicon which is treated by hydrochloric acid and hydrofluoric acid and then smelted, decontaminated and purified is 99.84-99.95%. Therefore, the method provided by the invention can recycle the silicon mud, and the purity of the recycled silicon ingot is higher, so that the development of producing high-purity silicon by utilizing the recycled silicon mud is greatly promoted.
Detailed Description
The main object of the present invention is to provide a method for purifying cut silicon sludge to obtain high purity silicon. Aiming at the defects of the prior art, the invention provides innovation of an acid treatment mode of the silicon mud, and selection of a selective reagent, and aims to obtain high-purity silicon and realize high optimization of a pretreatment process of cutting the silicon mud. Firstly, removing organic matters, silicon dioxide and other impurities in the silicon mud through three different modes of rinsing, acid treatment, primary acid treatment and secondary acid treatment, and then smelting, impurity removing and purifying the silicon powder through an electric arc furnace, so that a high-purity compact silicon ingot is obtained. Through detection, the purity of the high-purity silicon which is treated by hydrochloric acid and hydrofluoric acid and then smelted, decontaminated and purified is 99.84-99.95%. Therefore, in the technical scheme disclosed by the patent, the silicon mud can be recovered, and the purity of the recovered silicon ingot is higher, so that the development of producing high-purity silicon by utilizing the recovered silicon mud is greatly promoted. The specific test procedure is as follows:
and (one) rinsing and acid treatment:
Adding high-purity water into the initial silicon mud to prepare suspension with certain concentration, performing ultrasonic dispersion, and then performing filtering operation on the suspension to obtain filter residue A;
adding a prepared hydrochloric acid solution into the obtained filter residue A for pickling, then carrying out negative pressure suction filtration on the pickled solution by using a filter membrane, wherein the filter membrane is the pickled silicon mud, the filter membrane is the waste liquid, and a rinsing and acid treatment sample obtained by a wet method is collected for standby;
wherein the volume concentration of the hydrochloric acid is 5-15%;
Wherein, waste gas generated in the pickling process can be recovered in the pickling process;
And transferring the solid of the rinsing and acid treatment sample obtained by the wet method into an electric arc furnace for smelting, impurity removal and purification to obtain the high-purity silicon.
(II) one-stage acid treatment:
And directly adding the prepared hydrochloric acid solution into the initial silicon mud for pickling, and carrying out negative pressure suction filtration to obtain a section of acid treatment sample.
Wherein the volume concentration of the hydrochloric acid is 5-15%;
Wherein, waste gas generated in the pickling process can be recovered in the pickling process;
And transferring the solid of the first-stage acid treatment sample obtained by the wet method into an electric arc furnace for smelting, impurity removing and purifying to obtain the high-purity silicon.
(III) two-stage acid treatment:
Directly adding a prepared mixed solution into the initial silicon mud for pickling, wherein the mixed solution comprises hydrochloric acid and hydrofluoric acid solution, and carrying out negative pressure suction filtration to obtain a second-stage acid treatment sample;
wherein the volume concentration of the hydrochloric acid is 5-15%; the volume concentration of the hydrofluoric acid solution is 5-15%;
Wherein, waste gas generated in the pickling process can be recovered in the pickling process;
And transferring the two-stage acid treatment sample solid obtained by the wet method into an electric arc furnace for smelting, impurity removing and purifying to obtain the high-purity silicon.
And (3) sending samples obtained by the three methods to be checked, and determining the purity of the sample silicon obtained by different acid treatment modes. The three treatment methods are compared, and the purity of the silicon ingot obtained by smelting, impurity removing and purifying by adopting the second-stage acid treatment of the mixed solution of hydrochloric acid and hydrofluoric acid is highest and reaches 99.84% -99.95%.
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1:
Rinsing + acid treatment: 500g of initial silicon mud is taken, high-purity water is added into the initial silicon mud to prepare suspension, the suspension is dispersed by ultrasonic, and then the suspension is filtered to obtain filter residues. And then adding 1L of hydrochloric acid solution with the volume concentration of 10% into the obtained filter residues for pickling, carrying out negative pressure suction filtration on the pickled solution by using a filter membrane with the volume concentration of 0.22 mu m, obtaining silicon mud after pickling on the filter membrane, obtaining waste liquid below the filter membrane, collecting a rinsing and acid treatment sample obtained by a wet method, cleaning and drying, and carrying out smelting impurity removal and purification in an electric arc furnace to obtain the silicon ingot. The silicon ingot purity was calculated by testing its Al, B, ca, cu, fe, mg, mn, mo, ni, P, ti element content using inductively coupled plasma-mass spectrometry (ICP-MS).
Example 2:
And (3) acid treatment: the prepared 1L hydrochloric acid solution with the volume concentration of 10% is added into 500g of initial silicon mud for pickling, and a section of acid treatment sample is obtained through negative pressure suction filtration. Cleaning, drying, and smelting, impurity removing and purifying in an electric arc furnace to obtain silicon ingots. The silicon ingot purity was calculated by testing its Al, B, ca, cu, fe, mg, mn, mo, ni, P, ti element content using inductively coupled plasma-mass spectrometry (ICP-MS).
Example 3:
Two-stage acid treatment: and (3) adding 1L of prepared mixed solution into 500g of initial silicon mud for pickling, wherein the mixed solution comprises 10% hydrochloric acid with volume concentration and 15% hydrofluoric acid with volume concentration, and carrying out negative pressure suction filtration to obtain a second-stage acid treatment sample. Cleaning, drying, and smelting, impurity removing and purifying in an electric arc furnace to obtain silicon ingots. The silicon ingot purity was calculated by testing its Al, B, ca, cu, fe, mg, mn, mo, ni, P, ti element content using inductively coupled plasma-mass spectrometry (ICP-MS).
The comparative experiment results are shown in the following table:
From the above table data, the two-stage acid treatment of example 3 showed the best treatment effect on the silicon sludge, and the purity of the silicon ingot obtained by smelting, impurity removal and purification after the treatment was 99.95%, indicating that the mixed solution of hydrochloric acid and hydrofluoric acid was a better selective solvent for the silicon sludge treatment step. Wherein the hydrochloric acid is mainly used for improving the acid environment of the solution, and meanwhile, the hydrochloric acid can react with some basic impurity ions in the silicon mud, such as iron ions, copper ions and the like to form corresponding chlorides and accelerate the removal of impurities. Hydrofluoric acid can effectively dissolve impurities which cannot be removed by hydrochloric acid, mainly because hydrofluoric acid has good coordination and can form stable coordination compounds with metal ions, and the impurities are removed by water washing. Meanwhile, the hydrofluoric acid can remove silicon dioxide on the surface of the silicon powder and an oxide film on the surface of the metal impurity so as to enable the impurity to react more thoroughly.
Therefore, the invention provides an innovative method for treating 500g of silicon mud acid, and aims to purify and cut silicon mud so as to obtain high-purity silicon ingots.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (4)
1. A method for purifying cut silicon sludge for preparing high purity silicon, comprising the steps of:
(1) Adding the prepared mixed solution into the initial silicon mud for pickling; the mixed solution comprises hydrochloric acid and hydrofluoric acid solution, and a second-stage acid treatment sample is obtained through negative pressure suction filtration;
(2) And transferring the obtained two-stage acid treatment sample solid into an electric arc furnace for smelting, impurity removing and purifying to obtain the high-purity silicon.
2. The method for producing high purity silicon by purifying cut silicon slurry according to claim 1, wherein in step (1), the volume concentration of hydrochloric acid is 5 to 15%.
3. The method for producing high purity silicon by purifying a cut silicon slurry according to claim 1, wherein in step (1), the volume concentration of the hydrofluoric acid solution is 5 to 15%.
4. The method for producing high purity silicon from purified cut silicon slurry of claim 1 wherein step (1) further comprises recovering off-gas generated during the pickling process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311715990.2A CN117945405A (en) | 2023-12-14 | 2023-12-14 | Method for preparing high-purity silicon by purifying cut silicon mud |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311715990.2A CN117945405A (en) | 2023-12-14 | 2023-12-14 | Method for preparing high-purity silicon by purifying cut silicon mud |
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| Publication Number | Publication Date |
|---|---|
| CN117945405A true CN117945405A (en) | 2024-04-30 |
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| CN202311715990.2A Pending CN117945405A (en) | 2023-12-14 | 2023-12-14 | Method for preparing high-purity silicon by purifying cut silicon mud |
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- 2023-12-14 CN CN202311715990.2A patent/CN117945405A/en active Pending
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