CN115193101B - Method for recovering wire cutting cooling liquid - Google Patents
Method for recovering wire cutting cooling liquid Download PDFInfo
- Publication number
- CN115193101B CN115193101B CN202110383549.3A CN202110383549A CN115193101B CN 115193101 B CN115193101 B CN 115193101B CN 202110383549 A CN202110383549 A CN 202110383549A CN 115193101 B CN115193101 B CN 115193101B
- Authority
- CN
- China
- Prior art keywords
- cooling liquid
- silicon powder
- adsorption material
- waste
- regenerated
- 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.)
- Active
Links
- 239000000110 cooling liquid Substances 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000005520 cutting process Methods 0.000 title claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 133
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 109
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000000463 material Substances 0.000 claims abstract description 93
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000002699 waste material Substances 0.000 claims abstract description 74
- 238000011084 recovery Methods 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims description 56
- 239000003513 alkali Substances 0.000 claims description 37
- 239000003957 anion exchange resin Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 18
- 238000003825 pressing Methods 0.000 claims description 12
- 239000002826 coolant Substances 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 238000005496 tempering Methods 0.000 claims description 3
- 239000002594 sorbent Substances 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 13
- 238000011069 regeneration method Methods 0.000 abstract description 13
- 229910052710 silicon Inorganic materials 0.000 abstract description 13
- 239000010703 silicon Substances 0.000 abstract description 13
- 229910003460 diamond Inorganic materials 0.000 abstract description 9
- 239000010432 diamond Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000002173 cutting fluid Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- -1 silicon powder compound Chemical class 0.000 description 3
- 239000012809 cooling fluid Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28D—WORKING STONE OR STONE-LIKE MATERIALS
- B28D7/00—Accessories specially adapted for use with machines or devices of the preceding groups
- B28D7/02—Accessories specially adapted for use with machines or devices of the preceding groups for removing or laying dust, e.g. by spraying liquids; for cooling work
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/037—Purification
Abstract
The invention provides a wire cutting cooling liquid recovery method, which comprises the following steps: separating silicon powder in the waste cooling liquid to obtain a composite containing the silicon powder and desilication cooling liquid; and then respectively treating the compound and the desilication cooling liquid to obtain silica powder mud and regenerated cooling liquid. The method is particularly suitable for large-flux regeneration treatment of the cooling liquid for slicing the ultrathin silicon single crystal diamond wire and high-yield recovery of the ultrathin silicon powder, can obtain high-quality regenerated cooling liquid and high-purity ultrathin silicon powder mud, has large treatment capacity and good recovery effect, can continuously and efficiently recycle the regenerated cooling liquid, the ultrathin silicon powder mud and the adsorption material, and has low overall operation cost which is only 1/4-1/5 of that of the prior art; the recovery rate of the whole silicon powder reaches more than 84 percent, and the conductivity of the obtained regenerated cooling liquid is 17.7-19.4 mu S/cm, and the surface tension is 31.8-33.1mN/m.
Description
Technical Field
The invention belongs to the technical field of silicon single crystal wire cutting, and particularly relates to a wire cutting cooling liquid recovery method.
Background
The integrated circuit industry is the most important high and new technology for promoting national economy and social informatization development, and monocrystalline silicon wafers are widely applied to the manufacturing process of integrated circuits as the most commonly used semiconductor materials. At present, most of ultra-thin silicon single crystal cutting adopts a diamond wire cutting mode, and in the diamond wire cutting process, expensive cooling liquid with excellent suspending capacity, dispersing capacity, lubricating performance and cooling performance is required to be used so as to ensure that the cut silicon wafer has good repeatability, excellent quality and stability.
However, in the actual production process, along with the acceleration of the thinning process and the continuous improvement of the productivity, the superfine silicon powder (d) enters a linear cutting cooling liquid circulation system 50 =0.8 μm), resulting in a lot of dirty silicon wafer, resulting in an increase in the production cost of the post-dicing process; and the silicon-containing waste liquid has high organic matter content, and the random discharge can bring huge damage to the environment. Therefore, how to design a recovery method of the wire cutting cooling liquid so as to realize the regeneration of the cooling liquid and the recovery of the superfine silicon powder is a great economic benefit and an environmental benefit.
The main component of the cooling liquid is pure water, and the waste cooling liquid after cutting contains a large amount of silicon powder, and the silicon powder has extremely fine granularity and certain viscosity, and the actual separation requirements are difficult to be met by adopting solid/liquid separation methods such as centrifugation, floatation, filtration and the like. The chemical method, such as adding flocculant, can reduce the content of superfine silicon powder, but also destroy the effective components in the cooling liquid, increase the consumption of stock solution of the cutting liquid, and increase the production cost. Removing part of silicon powder in the cooling waste liquid by adopting a filter pressing method, and then mixing the filter pressing liquid with other cooling waste liquid for recycling; although the method does not destroy the effective components of the cooling liquid, the processing capacity and the efficiency are low, the requirement of capacity improvement is difficult to meet, and the occupied area of filter press equipment is large.
Chinese patent publication CN101982536A proposes a method for recovering silicon carbide and polyethylene glycol cutting fluid from silicon wafer cutting waste liquid, but the method is suitable for processing by using mortar cutting before 2010, and the current solar silicon wafer is processed by adopting a diamond wire cutting mode, wherein the diamond wire cutting mode mainly adopts cooling fluid, the main component of the current cooling fluid is polyether, and the patent publication adopts polyethylene glycol cutting fluid which is not suitable for the technical field of the current solar cutting, and the two cutting fluids are completely different two substances; the circulation collection mode of the polyethylene glycol cutting fluid is not suitable for the existing diamond wire cutting mode.
Chinese patent publication No. CN106865552A proposes a method for recovering high purity silicon powder from cutting waste slurry of crystalline silicon, which has limitation on boards involved in cutting, but does not contain aluminum oxide or calcium oxide, and the invention has no limitation requirements on relevant materials of the boards. In addition, the method adopts an organic flocculant, which is favorable for recovering silicon powder, but is unfavorable for reutilization of cooling liquid, and organic matters are difficult to separate when entering a cooling liquid system, so that the reutilization of the cooling liquid is influenced.
Chinese patent publication CN111015988A proposes a method for reusing cooling slurry in silicon wafer cutting, but this method only provides a theoretical recovery mode, and does not describe a recovery scheme or mention recovery of silicon powder.
Therefore, developing a new method with high efficiency and low cost to simultaneously realize the regeneration of the cooling liquid and the recovery of the superfine silicon powder is a production problem to be solved.
Disclosure of Invention
The invention provides a method for recovering wire cutting cooling liquid, which is particularly suitable for recovering cooling liquid for ultra-thin silicon single crystal cutting, and solves the technical problem that the cooling liquid regeneration and the ultra-thin silicon powder recovery cannot be simultaneously obtained in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for recovering wire cutting cooling liquid comprises the following steps:
separating silicon powder in the waste cooling liquid to obtain a composite containing the silicon powder and desilication cooling liquid;
and then the desilication cooling liquid and the compound are respectively treated to obtain regenerated cooling liquid and silica powder mud.
Further, the step of separating the silicon powder in the waste cooling liquid comprises the following steps:
adding an adsorption material into the waste cooling liquid to mix and stir, wherein the adsorption material adsorbs silicon powder in the waste cooling liquid to form the waste cooling liquid with adsorption material-silicon powder compound;
and then carrying out solid/liquid separation on the stirred waste cooling liquid to obtain the compound and the desilication cooling liquid respectively.
Further, the means for solid/liquid separation of the waste cooling liquid after agitation includes centrifugal separation or filtration separation.
Further, the adsorption material is anion exchange resin, and the particle size of the adsorption material is 150-1200 mu m; the weight specific gravity of the adsorption material is 0.5-5.3g/cm 3 。
Further, performing the treatment of the desilication cooling liquid includes:
placing anion exchange resin with a bed structure into the desilication cooling liquid to adsorb chloride ions in the desilication cooling liquid so as to obtain the regenerated cooling liquid;
the volume ratio of the anion exchange resin of the bed structure to the desilication cooling liquid is 1:150-250.
Further, the anion exchange resin of the bed structure after adsorption is mixed with alkali liquor with the mass fraction of 4-6wt.%, and regenerated anion exchange resin can be obtained; the regenerated anion exchange resin can be added as the adsorbent material to the spent coolant for reuse.
Further, performing a treatment of the composite includes:
adding the compound into alkali liquor with the mass fraction of 4-6wt.%, stirring and tempering to desorb the adsorption material and the silicon powder, and obtaining a mixture formed by the desorbed solid adsorption material and the solid silicon powder;
and then carrying out solid/solid separation on the mixture to obtain an alkali liquor adsorption material and alkali liquor silicon powder respectively.
Further, the separated alkali liquor adsorption material is added into 4-6wt.% acid liquor with mass fraction and stirred, so as to obtain regenerated adsorption material.
Further, the regenerated adsorbent material is added to the spent coolant for reuse.
Further, the separated alkali liquor silica powder is subjected to filter pressing dehydration to obtain silica powder mud, and other waste liquid is discharged into a sewage treatment system.
The recovery method designed by the invention is especially suitable for large-flux regeneration treatment of the cooling liquid for slicing the ultrathin silicon single crystal diamond wire and high-yield recovery of the ultrathin silicon powder, can obtain high-quality regenerated cooling liquid and high-purity ultrathin silicon powder mud, has large treatment capacity and good recovery effect, can continuously and efficiently recycle the obtained regenerated cooling liquid, ultrathin silicon powder mud and adsorption materials, and has low overall operation cost which is only 1/4-1/5 of that of the prior art.
The recovery rate of the whole silicon powder reaches more than 84 percent, and the conductivity of the obtained regenerated cooling liquid is 17.7-19.4 mu S/cm, and the surface tension is 31.8-33.1mN/m. Especially when the feeding amount of the adsorption material is 7g/L, the separation effect is best, the recovery rate of the superfine silicon powder reaches more than 90 percent, and the conductivity of the regenerated cooling liquid is not less than 18 mu S/cm.
Drawings
FIG. 1 is a flow chart of a method for recovering a wire cutting coolant in accordance with an embodiment of the present invention.
In the figure:
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The embodiment provides a wire cutting cooling liquid recovery method, which mainly adopts a recovery method combining induction adsorption, solid/liquid separation, ion exchange and solid/solid separation processes, is particularly suitable for large-flux regeneration treatment of cooling liquid for ultrathin silicon single crystal diamond wire slicing and high-yield recovery of superfine silicon powder, can obtain high-quality regenerated cooling liquid and high-purity superfine silicon powder mud, has high treatment capacity and good recovery effect, can continuously and efficiently recycle the obtained regenerated cooling liquid, superfine silicon powder mud and adsorption materials, and has low overall operation cost which is only 1/4-1/5 of the method in the prior art. The method comprises the following steps:
and separating the silicon powder in the waste cooling liquid to obtain a composite containing the silicon powder and desilication cooling liquid.
And then the desilication cooling liquid and the compound are respectively treated to obtain regenerated cooling liquid and silica powder mud.
Specifically, the step of separating the silicon powder in the waste cooling liquid comprises the following steps:
adding the adsorbent material into the waste cooling liquid, mixing and stirring, wherein the adsorbent material is anion exchange resin with particle diameter of 150-1200 μm and self weight specific gravity of 0.5-5.3g/cm 3 . The surface of the adsorption material has a certain amount of positive charges, and only chloride ions with corresponding electric charge quantity are released when the adsorption material adsorbs superfine silicon powder in the waste cooling liquid, but no other substances are released. After mixing and stirring, the silicon powder in the waste cooling liquid is promoted to be quickly agglomerated and settled, and the adsorption material adsorbs the silicon powder in the waste cooling liquid to form the waste cooling liquid with adsorption material-silicon powder compound solid.
And then carrying out solid/liquid separation on the stirred waste cooling liquid with the solid of the adsorption material-silicon powder compound so as to obtain the solid of the adsorption material-silicon powder compound and the desilication cooling liquid respectively.
Preferably, the solid/liquid separation of the stirred waste cooling liquid comprises centrifugal separation or filtration separation, and other separation modes can be adopted, and the method is within the scope of protection of the scheme.
Further, performing a treatment of the desilication coolant includes:
and placing the anion exchange resin with the bed structure into desilication cooling liquid to adsorb chloride ions in the desilication cooling liquid, thereby obtaining regenerated cooling liquid. The volume ratio of the anion exchange resin of the bed layer structure to the desilication cooling liquid is 1:150-250. After chloride ions in the desilication cooling liquid are removed by anion exchange resin with a bed structure, the conductivity of the cooling liquid can be reduced to a recycling standard, and the high-quality regenerated cooling liquid is obtained.
Mixing the anion exchange resin with the absorbed bed structure with alkali liquor with the mass fraction of 4-6wt.%, and obtaining regenerated anion exchange resin; the regenerated anion exchange resin and the adsorption material have the same components and can be reused as the adsorption material to be added into the waste cooling liquid again.
Further, performing a treatment of the adsorbent material-silica fume composite solid includes:
adding the adsorption material-silicon powder composite solid into alkali liquor with the mass fraction of 4-6wt.%, stirring and tempering to desorb the adsorption material and the silicon powder, and obtaining a desorbed mixture formed by the solid adsorption material and the solid silicon powder.
And then carrying out solid/solid separation on the desorbed mixture to obtain alkali liquor adsorption material and alkali liquor silicon powder respectively.
Adding the separated alkali liquor adsorption material into 4-6wt.% acid liquor, and stirring to obtain regenerated adsorption material. The regenerated adsorbent material is returned to be re-added to the spent coolant for reuse.
And (3) performing filter pressing dehydration on the separated alkali liquor silica powder to obtain recoverable silica powder mud, and discharging other waste liquid and waste into a sewage treatment system for treatment.
Several embodiments are specifically described below:
example 1:
and (3) placing 7.0g of the adsorption material into 1000mL of waste cooling liquid, mixing and stirring for 120s to uniformly disperse the adsorption material, so as to promote the silicon powder in the waste cooling liquid to quickly agglomerate and settle, and forming the waste cooling liquid with the adsorption material-silicon powder composite solid.
Transferring the waste cooling liquid containing the adsorption material-silicon powder compound into a centrifugal machine, treating for 20s at a rotating speed of 3000rpm, and respectively obtaining desilication cooling liquid and adsorption material-silicon powder compound solid after the centrifugation is finished.
And (3) mixing and separating 1000mL of separated desilication cooling liquid by 50mL of anion exchange resin with a bed structure to obtain regenerated cooling liquid and anion exchange resin with the bed structure after adsorption, mixing the anion exchange resin with the bed structure after adsorption with alkali liquor with the mass fraction of 4-6wt.%, and then returning to be mixed with waste cooling liquid, and then adsorbing silicon powder in the waste cooling liquid. The regenerated cooling liquid obtained was found to have a pH of 6.6, a conductivity of 18.0. Mu.S/cm, a surface tension of 32.3mN/m, a Chemical Oxygen Demand (COD) of 34350mg/L and a solid content of 0.006%.
And (3) adding 30g of separated solid of the adsorption material-silicon powder compound into alkali liquor with the volume of 40mL and the mass fraction of 4%, stirring for 5min, desorbing the silicon powder and the adsorption material, and separating the silicon powder and the adsorption material by adopting a rotary vibration sieve, wherein the recovery rate of the obtained adsorption material is 99.9%.
Adding 7g of the separated adsorption material into acid liquor with the volume of 20mL and the mass fraction of 4%, and stirring for 10min to realize regeneration of the adsorption material and obtain regenerated adsorption material; and (3) performing filter pressing dehydration on the separated alkali liquor containing the silica powder, and recovering the silica powder to obtain the silica powder with the recovery rate of 99.4%.
Example 2
And (3) placing 7.0g of the adsorption material into 1000mL of waste cooling liquid, mixing and stirring for 60s to uniformly disperse the adsorption material, so as to promote the silicon powder in the waste cooling liquid to quickly agglomerate and settle, and forming the waste cooling liquid with the adsorption material-silicon powder composite solid.
Transferring the waste cooling liquid containing the adsorption material-superfine silicon powder compound into a centrifugal machine, treating for 20s at the rotating speed of 2500rpm, and respectively obtaining desilication cooling liquid and adsorption material-silicon powder compound solid after the centrifugation is finished.
And (3) mixing and separating 1000mL of separated desilication cooling liquid by 50mL of anion exchange resin with a bed structure to obtain regenerated cooling liquid and anion exchange resin with the bed structure after adsorption, mixing the anion exchange resin with the bed structure after adsorption with alkali liquor with the mass fraction of 4-6wt.%, and then returning to be mixed with waste cooling liquid, and then adsorbing silicon powder in the waste cooling liquid. The regenerated cooling liquid obtained was found to have a pH of 6.4, a conductivity of 19.4. Mu.S/cm, a surface tension of 31.8mN/m, a Chemical Oxygen Demand (COD) of 33145mg/L and a solid content of 0.26%.
And (3) adding 30g of separated solid of the adsorption material-silicon powder compound into alkali liquor with the volume of 40mL and the mass fraction of 4%, stirring for 5min, desorbing silicon powder and the adsorption material, and separating the silicon powder and the adsorption material by adopting a rotary vibration sieve, wherein the recovery rate of the obtained adsorption material is 99.9%.
Adding 7g of the separated adsorption material into acid liquor with the volume of 20mL and the mass fraction of 4%, and stirring for 10min to realize the regeneration of the adsorption material to obtain regenerated adsorption material; and (3) performing filter pressing dehydration on the separated alkali liquor containing the silica powder, and recovering the silica powder to obtain the silica powder with the recovery rate of 90.6%.
Example 3
And (3) placing 7.0g of the adsorption material into 1000mL of waste cooling liquid, mixing and stirring for 120s to uniformly disperse the adsorption material, and promoting the silicon powder in the waste cooling liquid to quickly agglomerate and settle to form the waste cooling liquid with the adsorption material-silicon powder composite solid.
Transferring the waste cooling liquid containing the adsorption material-superfine silicon powder compound into a centrifugal machine, treating for 30s at the rotating speed of 2500rpm, and respectively obtaining desilication cooling liquid and adsorption material-silicon powder compound solid after the centrifugation is finished.
Passing 1000mL of separated desilication cooling liquid through 50mL of anion exchange resin with bed structure
And (3) mixing and separating to obtain regenerated cooling liquid and anion exchange resin with the adsorbed bed structure, mixing the anion exchange resin with the adsorbed bed structure with alkali liquor with the mass fraction of 4-6wt.%, and then returning to be mixed with waste cooling liquid, and then adsorbing silicon powder in the waste cooling liquid. The regenerated cooling liquid obtained was found to have a pH of 6.5, a conductivity of 18.2. Mu.S/cm, a surface tension of 32.1mN/m, a Chemical Oxygen Demand (COD) of 32748mg/L and a solid content of 0.21%.
And (3) adding 30g of separated solid of the adsorption material-silicon powder compound into alkali liquor with the volume of 40mL and the mass fraction of 4%, stirring for 5min to desorb the silicon powder and the adsorption material, and separating the silicon powder and the adsorption material by adopting a rotary vibration sieve to obtain the adsorption material with the recovery rate of 99.9%.
Adding 7g of the separated adsorption material into acid liquor with the volume of 20mL and the mass fraction of 4%, and stirring for 10min to realize regeneration of the adsorption material and obtain regenerated adsorption material; and (3) performing filter pressing dehydration on the separated alkali liquor containing the silica powder, and recovering the silica powder to obtain the silica powder with the recovery rate of 91.1%.
Example 4
And (3) placing 7.0g of the adsorption material into 1000mL of waste cooling liquid, mixing and stirring for 120s to uniformly disperse the adsorption material, and promoting the silicon powder in the waste cooling liquid to quickly agglomerate and settle to form the waste cooling liquid with the adsorption material-silicon powder composite solid.
Transferring the waste cooling liquid containing the adsorption material-silicon powder compound into a centrifugal machine, treating for 20s at 3500rpm, and respectively obtaining desilication cooling liquid and adsorption material-silicon powder compound solid after centrifugation.
And (3) mixing and separating 1000mL of separated desilication cooling liquid by 50mL of anion exchange resin with a bed structure to obtain regenerated cooling liquid and anion exchange resin with the bed structure after adsorption, mixing the anion exchange resin with the bed structure after adsorption with alkali liquor with the mass fraction of 4-6wt.%, and then returning to be mixed with waste cooling liquid, and then adsorbing silicon powder in the waste cooling liquid. The regenerated cooling liquid obtained was found to have a pH of 6.6, a conductivity of 17.9. Mu.S/cm, a surface tension of 32.0mN/m, a Chemical Oxygen Demand (COD) of 33379mg/L and a solid content of 0.005%.
And (3) adding 30g of separated solid of the adsorption material-silicon powder compound into alkali liquor with the volume of 40mL and the mass fraction of 4%, stirring for 5min, desorbing silicon powder and the adsorption material, and separating the silicon powder and the adsorption material by adopting a rotary vibration sieve, wherein the recovery rate of the obtained adsorption material is 99.9%.
Adding 7g of the separated adsorption material into acid liquor with the volume of 20mL and the mass fraction of 4%, and stirring for 10min to realize regeneration of the adsorption material and obtain regenerated adsorption material; and (3) performing filter pressing dehydration on the separated alkali liquor containing the silica powder, and recovering the silica powder to obtain the silica powder with the recovery rate of 99.3%.
Example 5
6.0g of the adsorption material is placed into 1000mL of waste cooling liquid, and the mixture is mixed and stirred for 120s to be uniformly dispersed, so that silicon powder in the waste cooling liquid is promoted to be quickly agglomerated and settled, and the waste cooling liquid with adsorption material-silicon powder compound solids is formed.
Transferring the waste cooling liquid containing the adsorption material-superfine silicon powder compound into a centrifugal machine, treating for 20s at a rotating speed of 3000rpm, and respectively obtaining desilication cooling liquid and adsorption material-silicon powder compound solid after the centrifugation is finished.
And (3) mixing and separating 1000mL of separated desilication cooling liquid by 50mL of anion exchange resin with a bed structure to obtain regenerated cooling liquid and anion exchange resin with the bed structure after adsorption, mixing the anion exchange resin with the bed structure after adsorption with alkali liquor with the mass fraction of 4-6wt.%, and then returning to be mixed with waste cooling liquid, and then adsorbing silicon powder in the waste cooling liquid. The regenerated cooling liquid obtained was found to have a pH of 6.8, a conductivity of 17.7. Mu.S/cm, a surface tension of 32.2mN/m, a Chemical Oxygen Demand (COD) of 34321mg/L and a solid content of 0.43%.
And (3) adding 30g of separated solid of the adsorption material-silicon powder compound into alkali liquor with the volume of 40mL and the mass fraction of 4%, stirring for 10min, desorbing the silicon powder and the adsorption material, and separating the silicon powder and the adsorption material by adopting a rotary vibration sieve, wherein the recovery rate of the obtained adsorption material is 99.9%.
Adding 7g of the separated adsorption material into acid liquor with the volume of 20mL and the mass fraction of 4%, and stirring for 10min to realize regeneration of the adsorption material and obtain regenerated adsorption material; and (3) performing filter pressing dehydration on the separated alkali liquor containing the silica powder, and recovering the silica powder to obtain the silica powder with the recovery rate of 84.7%.
Example 6
6.0g of the adsorption material is placed into 1000mL of waste cooling liquid, and the mixture is mixed and stirred for 120s to be uniformly dispersed, so that silicon powder in the waste cooling liquid is promoted to be quickly agglomerated and settled, and the waste cooling liquid with adsorption material-silicon powder compound solids is formed.
Transferring the waste cooling liquid containing the adsorption material-silicon powder compound into a centrifugal machine, treating for 30s at a rotating speed of 3000rpm, and respectively obtaining desilication cooling liquid and adsorption material-silicon powder compound solid after the centrifugation is finished.
And (3) mixing and separating 1000mL of separated desilication cooling liquid by 50mL of anion exchange resin with a bed structure to obtain regenerated cooling liquid and anion exchange resin with the bed structure after adsorption, mixing the anion exchange resin with the bed structure after adsorption with alkali liquor with the mass fraction of 4-6wt.%, and then returning to be mixed with waste cooling liquid, and then adsorbing silicon powder in the waste cooling liquid. The regenerated cooling liquid obtained was found to have a pH of 6.7, a conductivity of 18.4. Mu.S/cm, a surface tension of 33.1mN/m, a Chemical Oxygen Demand (COD) of 32645mg/L and a solid content of 0.38%.
And (3) adding 30g of separated solid of the adsorption material-silicon powder compound into alkali liquor with the volume of 40mL and the mass fraction of 4%, stirring for 10min, desorbing the silicon powder and the adsorption material, and separating the silicon powder and the adsorption material by adopting a rotary vibration sieve, wherein the recovery rate of the obtained adsorption material is 99.9%.
Adding 7g of the separated adsorption material into acid liquor with the volume of 20mL and the mass fraction of 4%, and stirring for 10min to realize regeneration of the adsorption material and obtain regenerated adsorption material; and (3) performing filter pressing dehydration on the separated alkali liquor containing the silica powder, and recovering the silica powder to obtain the silica powder with the recovery rate of 84.9%.
The technical parameters of the regenerated cooling liquid obtained by the method and the recovery rate of silicon powder are shown in table 1:
TABLE 1 recovery effect under different adsorption materials
From the analysis, the recovery rate of the whole silicon powder is more than 84%, the conductivity of the obtained regenerated cooling liquid is 17.7-19.4 mu S/cm, and the surface tension is 31.8-33.1mN/m. Especially when the feeding amount of the adsorption material is 7g/L, the separation effect is best, the recovery rate of the superfine silicon powder reaches more than 90 percent, and the conductivity of the regenerated cooling liquid is not less than 18 mu S/cm.
By adopting the recycling method designed by the invention, firstly, the adsorption material and superfine silica powder in the waste cooling liquid are fully mixed and stirred to generate an induced adsorption effect on the silica powder, so as to obtain an adsorption material-superfine silica powder compound; and then the waste cooling liquid with the adsorption material-superfine silica powder compound can be rapidly subjected to solid/liquid separation to obtain the separated cooling liquid without silica powder and the solid of the adsorption material-superfine silica powder compound, so that the silica powder in the waste cooling liquid is separated.
And then removing ions from the separated cooling liquid through an anion exchange bed resin bed, so that the conductivity of the deionized cooling liquid is reduced to a recycling standard, and a high-quality regenerated cooling liquid is obtained, and can be reused in wire cutting production, and finally the conductivity of the regenerated cooling liquid is obtained.
And sequentially carrying out desorption and solid/solid separation on the solid of the adsorption material-superfine silica powder compound to finally obtain the adsorption material and superfine silica powder respectively, wherein the adsorption material can be mixed with new non-cooling liquid for reuse, and the obtained superfine silica powder can be reused in other occasions.
The method is particularly suitable for large-flux regeneration treatment of the cooling liquid for slicing the ultrathin silicon single crystal diamond wires and high-yield recovery of the ultrathin silicon powder, can obtain high-quality regenerated cooling liquid and high-purity ultrathin silicon powder mud, has large treatment capacity and good recovery effect, can continuously and efficiently recycle the regenerated cooling liquid, the ultrathin silicon powder mud and the adsorption material, and has low overall operation cost which is only 1/4-1/5 of that of the prior art.
The foregoing detailed description of the embodiments of the invention has been presented only to illustrate the preferred embodiments of the invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (7)
1. The wire cutting cooling liquid recovery method is characterized by comprising the following steps of:
separating silicon powder in the waste cooling liquid to obtain a composite containing the silicon powder and desilication cooling liquid;
then the desilication cooling liquid and the compound are respectively treated to obtain regenerated cooling liquid and silica powder mud;
the step of separating the silicon powder in the waste cooling liquid comprises the following steps:
adding an adsorption material into the waste cooling liquid to mix and stir, wherein the adsorption material adsorbs silicon powder in the waste cooling liquid to form the waste cooling liquid with adsorption material-silicon powder compound;
carrying out solid/liquid separation on the stirred waste cooling liquid to obtain the compound and the desilication cooling liquid respectively;
the adsorption material is anion exchange resin;
performing the treatment of the desilication cooling liquid includes:
placing anion exchange resin with a bed structure into the desilication cooling liquid to adsorb chloride ions in the desilication cooling liquid so as to obtain the regenerated cooling liquid;
mixing the anion exchange resin of the bed structure after adsorption with alkali liquor with the mass fraction of 4-6wt.% to obtain regenerated anion exchange resin;
performing a treatment of the complex includes:
adding the compound into alkali liquor with the mass fraction of 4-6wt.%, stirring and tempering to desorb the adsorption material and the silicon powder, and obtaining a mixture formed by the desorbed solid adsorption material and the solid silicon powder;
carrying out solid/solid separation on the mixture to obtain alkali liquor adsorption material and alkali liquor silicon powder respectively;
adding the separated alkali liquor adsorption material into 4-6wt.% acid liquor, and stirring to obtain regenerated adsorption material;
and carrying out filter pressing dehydration on the separated alkali liquor silica powder to obtain the silica powder mud.
2. The method according to claim 1, wherein the means for solid/liquid separation of the waste cooling liquid after stirring comprises centrifugal separation or filtration separation.
3. The method for recovering a wire cutting coolant according to claim 1 or 2, wherein the particle diameter thereof is 150 to 1200 μm; the weight specific gravity of the adsorption material is 0.5-5.3g/cm 3 。
4. A wire cutting coolant recovery method as claimed in claim 3, wherein the volume ratio of the anion exchange resin of the bed structure to the desilication coolant is 1:150-250.
5. The method of claim 4, wherein said regenerated anion exchange resin is added as said adsorbent material to said spent coolant for reuse.
6. A wire cut coolant recovery method according to any one of claims 1-2, 4-5, wherein the regenerated sorbent material is added to the spent coolant for reuse.
7. The method for recycling linear cutting cooling liquid according to claim 6, wherein other waste liquid obtained after the separated alkali silicon powder is subjected to filter pressing dehydration is discharged into a sewage treatment system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110383549.3A CN115193101B (en) | 2021-04-09 | 2021-04-09 | Method for recovering wire cutting cooling liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110383549.3A CN115193101B (en) | 2021-04-09 | 2021-04-09 | Method for recovering wire cutting cooling liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115193101A CN115193101A (en) | 2022-10-18 |
| CN115193101B true CN115193101B (en) | 2024-02-13 |
Family
ID=83570972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110383549.3A Active CN115193101B (en) | 2021-04-09 | 2021-04-09 | Method for recovering wire cutting cooling liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115193101B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007097046A1 (en) * | 2006-02-24 | 2007-08-30 | Ihi Compressor And Machinery Co., Ltd. | Method and apparatus for treating silicon particle |
| CN101792142A (en) * | 2009-12-31 | 2010-08-04 | 唐康宁 | Method for recovering polysilicon ingots, carborundum powder and polyethylene glycol from cutting waste mortar |
| DE102009016014B3 (en) * | 2009-04-02 | 2010-09-30 | Sunicon Ag | Process for the recovery of pure silicon |
| WO2010137228A1 (en) * | 2009-05-29 | 2010-12-02 | 信越半導体株式会社 | Method for cutting silicon ingot |
| CN101982536A (en) * | 2010-11-02 | 2011-03-02 | 林小妹 | Method for recovering silicon carbide and polyethylene glycol cutting fluid from waste silicon wafer cutting fluid |
| WO2011034224A1 (en) * | 2009-09-17 | 2011-03-24 | 주식회사 알에스씨 | Method for purifying waste silicon slurry |
| KR20110124724A (en) * | 2010-05-11 | 2011-11-17 | 에코사이클 가부시키가이샤 | Etching acid waste liquid disposal system, etching acid waste liquid disposal apparatus and etching acid waste liquid disposal method applied to the system and the apparatus |
| CN102642835A (en) * | 2012-04-19 | 2012-08-22 | 镇江环太硅科技有限公司 | Method for recovering silicon material from waste materials in cutting crystalline silicon by diamond wire |
| CN102746934A (en) * | 2012-07-23 | 2012-10-24 | 镇江浩宇能源新材料有限公司 | Method for recovering water-soluble cutting fluid from silicon wafer cutting fluid |
| CN204792698U (en) * | 2015-07-08 | 2015-11-18 | 内蒙古中环光伏材料有限公司 | Diamond wire cutting silicon chip coolant liquid recovery system |
| CN106281633A (en) * | 2016-08-17 | 2017-01-04 | 合肥耀贝软件开发有限公司 | A kind of novel monocrystal silicon cutting waste mortar recycling production technology |
| CN106865552A (en) * | 2016-10-26 | 2017-06-20 | 东北大学 | A kind of method that high-purity silicon powder is reclaimed in cutting waste material slurry from crystalline silicon |
| CN107384568A (en) * | 2017-06-17 | 2017-11-24 | 常州福隆工控设备有限公司 | A kind of recoverying and utilizing method of silicon chip dicing waste mortar |
| WO2019239067A1 (en) * | 2018-06-14 | 2019-12-19 | Rosi | Treatment process for recycling silicon ingot cutting waste |
| CN211662383U (en) * | 2019-11-15 | 2020-10-13 | 天津市环智新能源技术有限公司 | Large-size silicon wafer cutting device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101538827B1 (en) * | 2008-12-31 | 2015-07-22 | 엠이엠씨 싱가포르 피티이. 엘티디. | Methods to recover and purify silicon particles from saw kerf |
| US8734751B2 (en) * | 2011-06-12 | 2014-05-27 | Taiwan Water Recycle Technology Co., Ltd. | Method and apparatus for recycling and treating wastes of silicon wafer cutting and polishing processes |
| FR3058999B1 (en) * | 2016-11-24 | 2019-10-25 | Novasep Process | PURIFICATION PROCESS USING LOW GRANULOMETRY RESIN |
-
2021
- 2021-04-09 CN CN202110383549.3A patent/CN115193101B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007097046A1 (en) * | 2006-02-24 | 2007-08-30 | Ihi Compressor And Machinery Co., Ltd. | Method and apparatus for treating silicon particle |
| DE102009016014B3 (en) * | 2009-04-02 | 2010-09-30 | Sunicon Ag | Process for the recovery of pure silicon |
| WO2010137228A1 (en) * | 2009-05-29 | 2010-12-02 | 信越半導体株式会社 | Method for cutting silicon ingot |
| WO2011034224A1 (en) * | 2009-09-17 | 2011-03-24 | 주식회사 알에스씨 | Method for purifying waste silicon slurry |
| CN101792142A (en) * | 2009-12-31 | 2010-08-04 | 唐康宁 | Method for recovering polysilicon ingots, carborundum powder and polyethylene glycol from cutting waste mortar |
| KR20110124724A (en) * | 2010-05-11 | 2011-11-17 | 에코사이클 가부시키가이샤 | Etching acid waste liquid disposal system, etching acid waste liquid disposal apparatus and etching acid waste liquid disposal method applied to the system and the apparatus |
| CN101982536A (en) * | 2010-11-02 | 2011-03-02 | 林小妹 | Method for recovering silicon carbide and polyethylene glycol cutting fluid from waste silicon wafer cutting fluid |
| CN102642835A (en) * | 2012-04-19 | 2012-08-22 | 镇江环太硅科技有限公司 | Method for recovering silicon material from waste materials in cutting crystalline silicon by diamond wire |
| CN102746934A (en) * | 2012-07-23 | 2012-10-24 | 镇江浩宇能源新材料有限公司 | Method for recovering water-soluble cutting fluid from silicon wafer cutting fluid |
| CN204792698U (en) * | 2015-07-08 | 2015-11-18 | 内蒙古中环光伏材料有限公司 | Diamond wire cutting silicon chip coolant liquid recovery system |
| CN106281633A (en) * | 2016-08-17 | 2017-01-04 | 合肥耀贝软件开发有限公司 | A kind of novel monocrystal silicon cutting waste mortar recycling production technology |
| CN106865552A (en) * | 2016-10-26 | 2017-06-20 | 东北大学 | A kind of method that high-purity silicon powder is reclaimed in cutting waste material slurry from crystalline silicon |
| CN107384568A (en) * | 2017-06-17 | 2017-11-24 | 常州福隆工控设备有限公司 | A kind of recoverying and utilizing method of silicon chip dicing waste mortar |
| WO2019239067A1 (en) * | 2018-06-14 | 2019-12-19 | Rosi | Treatment process for recycling silicon ingot cutting waste |
| CN211662383U (en) * | 2019-11-15 | 2020-10-13 | 天津市环智新能源技术有限公司 | Large-size silicon wafer cutting device |
Non-Patent Citations (1)
| Title |
|---|
| 铁生年 ; 侯思懿 ; 汪长安 ; 王涛 ; .新能源硅产业碳化硅切割废料回收利用研究进展.科技导报.2013,(04),23-28. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115193101A (en) | 2022-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104176737B (en) | Method for recovering silicon powder from cut mortar waste | |
| CN104229906B (en) | The method and apparatus of the nickel-containing waste water preparation plating level single nickel salt utilizing surface treatment process to produce | |
| CN1227061C (en) | Ion separation using surface-treated xerogel | |
| CN1883787A (en) | Process for polyvinyl alcohol embedding preparation of spherical bentonite | |
| WO2011078219A1 (en) | Method for recovering purified silicon-containing powder | |
| CN110666178B (en) | Recovery processing method of additive manufacturing waste titanium or titanium alloy powder | |
| CN1162204C (en) | Exhaust gas desulfurizing method and system therefor | |
| CN102247933A (en) | Method for purifying silicon powder | |
| CN108179022A (en) | A kind of admiralty fuel oil compounding desulfurization filtering agent and its preparation method and application | |
| CN105664840A (en) | Modified aluminum salt adsorbent, preparation method and application thereof | |
| CN108579683B (en) | Sulfometalorganic framework UIO-66@ mSi-SO3Application of H material | |
| CN115193101B (en) | Method for recovering wire cutting cooling liquid | |
| CN102390832B (en) | Method for treating waste silicon powder produced in trichlorosilane synthesis process | |
| CN103397190B (en) | Method for producing high-purity gold and copper sulphate from gold-bearing copper sludge | |
| CN114477188A (en) | Method and device for purifying high-purity quartz sand | |
| CN101041496A (en) | Treatment method for drainge containing fluorin ion and drainge treating agent | |
| CN102229113A (en) | Method for recovering sapphire powder | |
| CN111573685A (en) | Method for preparing organobentonite from calcium-based bentonite raw soil in efficient and environment-friendly manner | |
| CN104194910B (en) | The solid-liquid separating method of crystal silicon chip cutting liquid | |
| CN1863591A (en) | Anion adsorbent, process for producing the same and method of water treatment | |
| CN217578798U (en) | Cooling liquid recycling system for silicon single crystal diamond wire slicing | |
| CN112725061B (en) | Method for separating sulfonate additive from waste lubricating oil | |
| CN102060299A (en) | Method for separating silica powder from impurities in mixture | |
| CN1210502A (en) | Method for extracting antimony from elemental phosphorus | |
| CN106966396A (en) | A kind of heavy-fluid and silicon and the separation method of carborundum for divided silicon and carborundum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |