CN104761080A - Treatment and utilization method of waste acid and waste alkali in electronic industry - Google Patents
Treatment and utilization method of waste acid and waste alkali in electronic industry Download PDFInfo
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- CN104761080A CN104761080A CN201510118533.4A CN201510118533A CN104761080A CN 104761080 A CN104761080 A CN 104761080A CN 201510118533 A CN201510118533 A CN 201510118533A CN 104761080 A CN104761080 A CN 104761080A
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Abstract
A treatment and utilization method of waste acid and waste alkali in electronic industry, which is characterized in that according to the properties of main components, including hydrofluoric acid (HF), sulfuric acid (H2SO4), hydrochloric acid (HCl) and sodium hydroxide (NaOH), with assistance of a phosphorization industry waste, fluorine-containing silicon dioxide. A chemical reaction method is employed at the normal temperature, under a normal pressure and at a low concentration for converting the components into available resources which is then separated. The rest process waste water is neutralized with calcium carbide slag and the pH value is regulated to 9.5-10.5 to remove residual fluorine. Iron salt is added to adsorb various impurities so that the impurities can be flocculated and deposited. Ca(OCl)2 is added for remove metal impurities. Finally, through filtering separation, the pH value is regulated and then the waste water reaches the standard and can be discharged.
Description
Technical field
The present invention relates to field of inorganic chemical engineering, particularly relate to the industrial fluorine-containing spent acid such as electronics, Waste Sulfuric Acid, waste hydrochloric acid, the utilization of spent caustic and method of disposal.
Background technology
Electronics, photovoltaic industry are the novel industries that China is being surging forward.In recent years, chinese Electronics Industry grows continuously and fast, the industries such as semi-conductor, unicircuit, photoelectricity, sun power, electromobile, from original " unknown to the public ", cross " coming out at the top ", China has become the world production base of the electronic components such as loud speaker, aluminium electrolutic capacitor, picture tube, printed circuit board, semiconductor separation part, particularly sun power has become production base the biggest in the world, the fast development of electron trade is that attracted attention in the world, but also carries pollutions maximum in the world at present.Need to carry out the art breading such as soda acid is washed, soda acid etching to metallic substance, silicon chip etc. in its production process, employ sulfuric acid, hydrochloric acid, hydrofluoric acid, sodium hydroxide etc. as treatment agent wherein in a large number, along with the performance degradation in its use procedure, its effect reduces gradually, finally becomes waste liquid.Its concentration (mass percent) is respectively hydrofluoric acid (HF) 8 ~ 15%, sulfuric acid (H
2sO
4) 20 ~ 40%, hydrochloric acid (HCL) 20 ~ 28%, sodium hydroxide (NaOH) 20 ~ 27%.
The problem that electronics photovoltaic industry makes us being concerned about, having a headache most is exactly the process problem of waste liquid in its production process.Make us it is of concern that because have available economic worth in waste liquid, headachy is that intractability is large, cost of disposal is high because waste liquid understands serious environment pollution for this reason.How to adopt the most directly, simple method, can recycle useful component wherein, can make again that waste liquid is disposable is manipulated so water up to standard discharge, be the pending difficult problem of urgency that current enterprise faces.
For the treatment process of acid solution, usual employing be neutralisation, i.e. lime method and lime salt iron processes, carry out neutralization reaction, sedimentation and sludge disposal, but useful composition wherein causes waste, and waste water is difficult to reach discharging standards, particularly fluorion and part metals positively charged ion still major part residue in waste water, cause nuisance to exceed standard, water quality color and luster is muddy.Suzhou Crystal Clear Chemical Co., Ltd.'s " Chinese patent: CN201310159484X " discloses and relates to the reuse of a kind of electron trade etch process and resource recycling and utilize technique and " Chinese patent: CV2013101545576 " electronic-grade mixed waste liquor to reclaim and recycle utilization, wherein nitric acid, hydrofluoric acid, silicofluoric acid in paper waste liquid, after refining and edulcoration, add high density salpeter solution or hydrofluoric acid solution through supplementing again, Concentration Modulation become usable acid and returns to production line and use.But extend with the production cycle, enterprise can not long-term supplementing and discharging without waste liquid, this discussion only has Application way and without waste liquid final disposal method.Hubei Tianjin Trade Co., Ltd.'s " Chinese patent: CN2009100621364 ", equally just carry out the discussion of the recycling of fluorine, fluorinion concentration in its waste liquid can be down to below 10mg/l, but other metallic impurity, suspended substance, colourity fail to reach emission request and waste liquid cost of disposal is high.In sum, for fluorine-containing spent acid, Waste Sulfuric Acid, waste hydrochloric acid, spent caustic that electron trade produces, adopt common in and method of disposal, both wasted available stock, waste liquid can not be made again to finish full harmlessness disposing; Adopt single-minded recycling, and do not do final waste liquid disposal, also fail fundamentally to solve problem of environmental pollution.And how to accomplish from then on to recycle its useful composition in waste liquid, can the treatment of wastes with processes of wastes against one another make waste liquid be manipulated so water up to standard discharge again, be the effective way that this patent can solve.
Summary of the invention
The object of the treatment and use method of a kind of electron trade spent acid of the present invention salkali waste is that the spent acid solution produced in electronics, photovoltaic industry production process, waste lye are carried out to joint disposal and utilize useful component wherein to make it " turn waste into wealth ", " treatment of wastes with processes of wastes against one another " solves environmental pollution problem, and invest little, simple to operate, processing cost is low, social benefit is remarkable.
In order to realize object of the present invention, applicant is through years of researches, and test, trial production, has invented a kind for the treatment of and use method of electron trade spent acid salkali waste.
The treatment and use method of a kind of electron trade spent acid of the present invention salkali waste is achieved in that according to hydrofluoric acid (HF), the sulfuric acid (H in this waste liquid main component
2sO
4), the character of hydrochloric acid (HCl), sodium hydroxide (NaOH), be aided with phosphatization industry waste fluorinated silicon dioxide, under normal temperature and pressure, lower concentration, adopt chemical reaction method, be translated into valuable cargo and be separated.Residue processing wastewater, adopts carbide slag to carry out neutralization reaction, and adjustment pH value to 9.5 ~ 10.5, to remove residual fluorine; Add molysite to make various impurity absorption, flocculating settling; Add Ca (OCl)
2to remove metallic impurity, after being separated by filtration, adjustment pH value, discharged wastewater met the national standard.
Present method adopts following treatment process:
1, concentration adjustment and auxiliary material are equipped with
concentration adjusts: concentration adjustment is intended to make follow-up each operation obtain the corresponding optimum response concentration of required various chemical substances and amount, to ensure the peak use rate of active chemical in waste liquid, the particularly recovery utilization rate of fluorine element, also makes the waste water of rear operation be convenient to dispose simultaneously.Namely hydrofluoric acid solution concentration to 8% ~ 10%(mass percent is adjusted), sulfuric acid concentration 20 ~ 30%(mass percent), concentration of hydrochloric acid 20 ~ 27%(mass percent), naoh concentration 16 ~ 28%(mass percent), when concentration Gao Shijun is diluted in this concentration range with water respectively, when the concentration is low then respectively with high density and its lower concentration Mixed adjustment in this concentration range.
auxiliary material is equipped with: its auxiliary material is the carbide slag deriving from the fluorine-containing white residue of phosphatization industry and produce with the calcium carbide route production enterprise such as polyvinyl chloride, vinyl acetate between to for plastic.Use fluorine-containing white residue, the aim of carbide slag is for reaching " treatment of wastes with processes of wastes against one another ", reduce the object of cost of disposal.
2, silicofluoric acid (H is produced
2siF
6): hydrofluoric acid (HF) and fluorine-containing white residue are reacted to generate silicofluoric acid (H
2siF
6):
By concentration 8 ~ 10%(mass percent) hydrofluoric acid is placed in stirred reactor, under agitation slowly adds fluorine-containing white residue.Its fluorine-containing white residue add-on adds 20 ~ 40% by the theoretical amount in reaction formula is excessive, reacts 30 minutes ~ 1 hour, then leaves standstill 8 ~ 10 hours, makes it fully react completely.
Its chemical equation is: 6HF+SiO
2-H
2siF
6+ 2H
2o.
3, extracting sulfuric acid sodium (Na
2sO
4):
The amount of corresponding goods and materials is added, by sulfuric acid (H by the molecular ratios in reaction formula
2sO
4) react to generate sodium sulfate (Na with salkali waste (NaOH)
2sO
4).
Its chemical reaction chemical equation is: H
2sO
4+ 2 NaOH-Na
2sO
4+ 2H
2o 4, produce sodium-chlor (NaCl):
Add the amount of corresponding goods and materials by the molecular ratios in reaction formula, hydrochloric acid (HCl) and salkali waste (NaOH) are reacted to generate sodium chloride nacl
Its chemical equation is: HCl+NaOH-NaCl+H
2o
5, Sodium Silicofluoride is produced:
By the silicofluoric acid (H that reaction generates
2siF
6) in the reactor, under agitation slowly add sodium sulfate (Na
2sO
4) solution or sodium-chlor (NaCl) solution, its sodium sulfate (Na
2sO
4) solution or (NaCl) solution adds 10 ~ 20% by the theoretical amount in reaction formula is excessive, to make F
-ion fully reacts and generates Sodium Silicofluoride (Na
2siF
6) crystalline deposit.The reactive crystallization time is 30-60 minute, leaves standstill 15-30 minute.Its chemical equation is
H
2SiF
6+ Na
2SO
4—Na
2SiF
6+ H
2SO
4H
2SiF
6+ 2NaCl—Na
2SiF
6+2HCl
6, filtering separation
Mother liquor reaction being generated Sodium Silicofluoride crystallization adopts the methods such as centrifugal or suction filtration to carry out solid-liquid separation, and obtain product Sodium Silicofluoride, its waste liquid enters processing wastewater processing links.
7, processing wastewater process
first waste acid water after filtering separation is carried out acid-base neutralisation disposal.
The refuse carbide slag that the neutralization reaction agent that the treatment and use method of a kind of electron trade spent acid of the present invention salkali waste adopts is discharged for the manufacturing enterprise such as generated by polyvinyl chloride by calcium carbide, vinyl acetate between to for plastic.Reach the treatment of wastes with processes of wastes against one another with it, reduce the object of cost of disposal.But wherein containing the objectionable impurities such as sulphur, arsenic, therefore do corresponding disposal in later stage wastewater treatment.
Adding carbide slag in neutralization reaction is excessive response, and adjustment pH value 9.5 ~ 10.5, to remove the residual fluorine in waste water, its fluorion precipitates with Calcium Fluoride (Fluorspan) form.
add the flocculating settlings such as molysite, wherein arsenic is with ferric arsenate (FeA
3o
4) form precipitation.Its add-on is determined according to the foreign matter content in waste liquid.
add Losantin (Ca (OCl)
2) to make the SO in waste water
2be oxidized to SO
3calcium sulfate precipitation is generated with milk of lime.
Ca (OCl) simultaneously
2react with water and generate hypochlorous acid (HOCl), the reactive chlorine (Cl in hypochlorous acid
-) there is very strong activity, thus by the Fe in waste water
2+be oxidized to Fe
3+, its principal reaction is as follows:
Ca(OCl)
2+2H
2O—Ca(OH)
2+2HOCl
3FeSO
4+3Cl—Fe(SO
4)
3+FeCl
3
Fe(SO
4)
3+3Ca(OH)
2—2Fe(OH)
3↓+3CaSO
4↓
2FeCl
3+3Ca(OH)
2—2Fe(OH)
2↓+3CaCl
2
Its add-on is determined according to the foreign matter content in waste liquid.
Above-mentioned Adding Way for add successively in retort.
filtering separation.Drainage detects rear discharge up to standard.
The feed composition of each step of reaction for the treatment of and use method of a kind of electron trade of the present invention spent acid salkali waste is (proportional concentration of each material composition and water is mass percent):
Resultant of reaction title material name concentration (mass percent) proportioning (weight part)
Silicofluoric acid (H
2siF
6): hydrofluoric acid (HF) 8-10% 10-12
Silicon-dioxide (SiO
2) 90-95% 0.5-0.7
Sodium sulfate (Na
2sO
4): sulfuric acid (H
2sO
4) 20-30% 3-5
Sodium hydroxide (NaOH) 16-28% 2.7-4.5
Sodium-chlor (NaCl): hydrochloric acid (HCl) 20-27% 2.5-4
Sodium hydroxide (NaOH) 16-28% 2.7-4.5
Sodium Silicofluoride (Na
2siF
6): silicofluoric acid (H
2siF
6) 8-11% 10-12
Sodium sulfate (Na
2sO
4) 17-22% 6-8
(or with) sodium-chlor (NaCl) 18-22% 5.0-7.0
The beneficial effect of the treatment and use method of a kind of electron trade spent acid of the present invention salkali waste is: the spent acid solution produced in electronics, photovoltaic industry production process, waste lye are carried out to joint disposal and utilize useful component wherein to make it " turn waste into wealth ", " treatment of wastes with processes of wastes against one another " solves environmental pollution problem, and invest little, simple to operate, processing cost is low, social benefit is remarkable.
Accompanying drawing explanation
Fig. 1 is the treatment and use method process flow sheet of a kind of electron trade spent acid of the present invention salkali waste.
Embodiment
Below the embodiment of the treatment and use method of a kind of electron trade spent acid of the present invention salkali waste is further described, but the present invention is not limited to following examples:
Embodiment 1:
produce silicofluoric acid (H
2siF
6)
Proportioning raw materials (concentration is mass percent)
Hydrofluoric acid (HF, concentration 8%) 10(kg)
Fluorine-containing white residue 0.56 (kg)
Above-mentioned hydrofluoric acid (HF) after carrying out concentration tune is dropped in the reactor that volume is 20L, slowly adds above-mentioned fluorine-containing white residue stirring reaction 30 minutes with it, leave standstill 10 hours, cross and filter excess silicon dioxide (SiO
2) etc. throw out, obtain silicofluoric acid (H
2siF
6) solution, for subsequent use.
extracting sulfuric acid sodium (Na
2sO
4)
Proportioning raw materials (concentration is mass percent)
Sulfuric acid (H
2sO
4concentration 20%) 3.8 (kg)
Sodium hydroxide (NaOH concentration 25%) 2.48 (kg)
Above-mentioned sodium hydroxide (NaOH) after carrying out concentration adjustment is dropped in the reactor that container is 20L, slowly adds the above-mentioned sulfuric acid (H after concentration adjustment
2sO
4) stirring reaction with it, obtain metabisulfite solution, for subsequent use.
produce Sodium Silicofluoride (Na
2siF
6):
A, chemical reaction: by above-mentioned
silicofluoric acid (the H produced
2siF
6) solution drop into volume be in the reactor of 30L, slowly add
sodium sulfate (the Na produced
2sO
4) solution carries out stirring reaction, the reaction times is 45 minutes, leaves standstill 15 minutes, crystallization.
B, filtering separation: by the mother liquor after above-mentioned reactive crystallization, adopt suction filtration method to carry out solid-liquid separation, and the crystalline solid after separation is obtained Sodium Silicofluoride finished product after drying, and its solution is processing wastewater and enters next step waste water dis posal operation.
wastewater treatment
Above-mentioned carrying out, in the input of the solution after filtering separation 50L reactor, is added carbide slag (Ca (OH) respectively
2), adjustment pH value to 9.5, then add molysite successively, Losantin Ca carries out stirring reaction, leaves standstill and 1 as a child carries out filtering separation, filtrate adjustment pH value is to neutral.
Its waste water dis posal situation detected result is as follows:
After waste water dis posal: containing F
-8.91mg/L
COD: 43.62 mg/L
PH value: 7.0
Colourity (extension rate): 50
Embodiment 2:
produce silicofluoric acid (H
2siF
6)
Proportioning raw materials (concentration is mass percent)
Hydrofluoric acid (HF. concentration 10%) 10 (kg)
Fluorine-containing white residue 0.65 (kg)
Above-mentioned hydrofluoric acid (HF) is dropped in the reactor that container is 20L, slowly adds above-mentioned fluorine-containing white residue stirring reaction 60 minutes.Leave standstill after 8 hours, cross and filter the throw outs such as excess silicon dioxide, obtain silicofluoric acid (H
2siF
6) solution, for subsequent use.
extracting sulfuric acid sodium (Na
2sO
4):
Proportioning raw materials (concentration is mass percent)
Sulfuric acid (H
2sO
4concentration 30%) 3.1 (kg)
Sodium hydroxide (NaOH concentration 20%) 3.8 (kg)
It is in the reactor of 20L that above-mentioned sodium hydroxide (NaOH) solution is dropped into volume, slowly adds above-mentioned sulfuric acid (H
2sO
4) solution stirring reaction acquisition metabisulfite solution with it, for subsequent use.
produce Sodium Silicofluoride (Na
2siF
6):
A, chemical reaction:
By above-mentioned
silicofluoric acid (the H produced
2siF
6) solution drop into 30L reactor in, slowly add
sodium sulfate (the Na produced
2sO
4) solution carries out stirring reaction, the reaction times is 60 minutes, leaves standstill 15 minutes crystallizations.
B, filtering separation:
By the mother liquor after above-mentioned reactive crystallization, vacuum filtration is utilized to carry out solid-liquid separation.Obtain finished product Sodium Silicofluoride, the solution after its filtration enters next step waste water dis posal operation.
waste water dis posal:
By in embodiment 1
waste water dis posal operation carries out waste water dis posal.
Its waste water dis posal situation detected result is as follows:
After waste water dis posal: containing F
-amount: 8.95mg/L
COD: 45.36 mg/L
PH value: 7
Colourity (extension rate): 50
Embodiment 3
produce silicofluoric acid (H
2siF
6) by example 1
method produces silicate fluoride solution
produce sodium-chlor (NaCl):
Proportioning raw materials (concentration is mass percent)
Hydrochloric acid (HCL concentration 20%) 2.5 (kg)
Sodium hydroxide (NaOH concentration 28%) 2 (kg)
It is in the reactor of 20L that above-mentioned hydrochloric acid (HCL) is dropped into solvent, slowly adds above-mentioned sodium hydroxide and carries out stirring reaction, obtained sodium chloride solution.
produce Sodium Silicofluoride (Na
2siF
6):
A, chemical reaction
By in enforcement 1
silicofluoric acid (the H produced
2siF
6) solution drop into volume be in the reactor of 30L, slowly add appeal
the sodium chloride solution produced carries out stirring reaction, and the reaction times is 30 minutes, leaves standstill 30 minutes, crystallization.
B, filtering separation
By the solution of above-mentioned reactive crystallization, adopt suction filtration method to carry out solid-liquid separation, after drying, obtained Sodium Silicofluoride finished product, the waste liquid after its filtration enters next step wastewater treatment operation in isolated crystallization.
wastewater treatment
By in enforcement 1
waste water dis posal operation carries out waste water dis posal, and its waste water dis posal detected result is as follows:
After waste water dis posal: containing F
-amount is: 8.92mg/L
COD: 43.64 mg/L
PH value: 7
Colourity (extension rate): 50
Embodiment 4
produce silicofluoric acid (H
2siF
6) by example 2
produce silicate fluoride solution.
produce sodium-chlor (NaCl)
Proportioning raw materials (concentration is mass percent)
Hydrochloric acid (HCL concentration 27%) 2.6 (kg)
Sodium hydroxide (NaOH concentration 20%) 3.80 (kg)
It is in the reactor of 20L that above-mentioned hydrochloric acid (HCl) is dropped into solvent, slowly adds above-mentioned sodium hydroxide and carries out stirring reaction, obtained sodium-chlor (NaCl) solution.
produce Sodium Silicofluoride (Na
2siF
6)
A, chemical reaction
By in enforcement 2
silicofluoric acid (the H produced
2siF
6) solution drop into volume be in the reactor of 30L, slowly add above-mentioned
the sodium chloride solution produced carries out stirring reaction, and the reaction times is 45 minutes, leaves standstill 20 minutes, crystallization.
B, filtering separation
Filtered by the solution of appeal reactive crystallization, after drying, obtained Sodium Silicofluoride finished product, the waste liquid after its filtration enters next step wastewater treatment operation in isolated crystallization.
wastewater treatment:
By in enforcement 1
waste water dis posal operation carries out waste water dis posal, and its waste water dis posal detected result is as follows:
After waste water dis posal: containing F
-amount: 8.93mg/L
COD: 43.61 mg/L
PH value: 7
Colourity (extension rate): 50.
Claims (9)
1. a treatment and use method for electron trade spent acid salkali waste, is characterized in that according to hydrofluoric acid (HF), the sulfuric acid (H in this waste liquid main component
2sO
4), the character of hydrochloric acid (HCl), sodium hydroxide (NaOH), be aided with phosphatization industry waste fluorinated silicon dioxide, under normal temperature and pressure, lower concentration, adopt chemical reaction method, be translated into valuable cargo and be separated; Residue processing wastewater, adopts carbide slag to carry out neutralization reaction, and adjustment pH value to 9.5 ~ 10.5, to remove residual fluorine; Add molysite to make various impurity absorption, flocculating settling; Add Ca (OCl)
2to remove metallic impurity, after being separated by filtration, adjustment pH value, discharged wastewater met the national standard.
2. the treatment and use method of a kind of electron trade spent acid salkali waste according to claim 1, it is characterized in that adjustment hydrofluoric acid solution concentration to 8% ~ 10%(mass percent), sulfuric acid concentration 20 ~ 30%(mass percent), concentration of hydrochloric acid 20 ~ 27%(mass percent), naoh concentration 16 ~ 28%(mass percent), when concentration Gao Shijun is diluted in this concentration range with water respectively, when the concentration is low then respectively with high density and its lower concentration Mixed adjustment in this concentration range.
3. the treatment and use method of a kind of electron trade spent acid salkali waste according to claim 1, is characterized in that its auxiliary material is for the carbide slag deriving from the fluorine-containing white residue of phosphatization industry and produce with the calcium carbide route production enterprise such as polyvinyl chloride, vinyl acetate between to for plastic.
4. the treatment and use method of a kind of electron trade spent acid salkali waste according to claim 1, is characterized in that hydrofluoric acid (HF) and fluorine-containing white residue to react to generate silicofluoric acid (H
2siF
6).
5. the treatment and use method of a kind of electron trade spent acid salkali waste according to claim 1, is characterized in that sulfuric acid (H
2sO
4) react to generate sodium sulfate (Na with salkali waste (NaOH)
2sO
4).
6. the treatment and use method of a kind of electron trade spent acid salkali waste according to claim 1, is characterized in that hydrochloric acid (HCl) and salkali waste (NaOH) to react to generate sodium chloride nacl.
7. the treatment and use method of a kind of electron trade spent acid salkali waste according to claim 1, is characterized in that silicofluoric acid (H reaction generated
2siF
6) in the reactor, under agitation slowly add sodium sulfate (Na
2sO
4) solution or sodium-chlor (NaCl) solution, its sodium sulfate (Na
2sO
4) solution or (NaCl) solution adds 10 ~ 20% by the theoretical amount in reaction formula is excessive, to make F
-ion fully reacts and generates Sodium Silicofluoride (Na
2siF
6).
8. the treatment and use method of a kind of electron trade spent acid salkali waste according to claim 1, is characterized in that mother liquor reaction being generated Sodium Silicofluoride crystallization adopts the methods such as centrifugal or suction filtration to carry out solid-liquid separation, obtains product Sodium Silicofluoride.
9. the treatment and use method of a kind of electron trade spent acid salkali waste according to claim 1, is characterized in that
first waste acid water after filtering separation is carried out acid-base neutralisation disposal
Adding carbide slag in neutralization reaction is excessive response, adjustment pH value 9.5 ~ 10.5, and to remove the residual fluorine in waste water, its fluorion precipitates with Calcium Fluoride (Fluorspan) form;
add the flocculating settlings such as molysite, wherein arsenic is with ferric arsenate (FeA
3o
4) form precipitation;
add Losantin (Ca (OCl)
2) to make the SO in waste water
2be oxidized to SO
3calcium sulfate precipitation is generated with milk of lime; Simultaneously by the Fe in waste water
2+be oxidized to Fe
3+.
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ID=53643246
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| CN106395831A (en) * | 2016-08-31 | 2017-02-15 | 池州西恩新材料科技有限公司 | Silicon wafer processing cleaning effluent resource recycling method |
| CN109678563A (en) * | 2019-01-17 | 2019-04-26 | 瓮福紫金化工股份有限公司 | A kind of method of waste acid recycling |
| CN110078261A (en) * | 2019-05-20 | 2019-08-02 | 中国恩菲工程技术有限公司 | Handle the method and system of waste water |
| CN110203885A (en) * | 2019-06-26 | 2019-09-06 | 福建中融科技有限公司 | The separation and regeneration technology of the waste hydrochloric acid of hydrofluoric acid containing |
| CN111203427A (en) * | 2020-01-13 | 2020-05-29 | 东江环保股份有限公司 | System and method for co-processing waste glass powder and pickling waste liquid |
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| CN101555017A (en) * | 2009-05-20 | 2009-10-14 | 湖北天进工贸有限公司 | Multi-grade comprehensive utilization technology of fluoride-contained waste acid in phosphating industry |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106395831A (en) * | 2016-08-31 | 2017-02-15 | 池州西恩新材料科技有限公司 | Silicon wafer processing cleaning effluent resource recycling method |
| CN109678563A (en) * | 2019-01-17 | 2019-04-26 | 瓮福紫金化工股份有限公司 | A kind of method of waste acid recycling |
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| CN111203427A (en) * | 2020-01-13 | 2020-05-29 | 东江环保股份有限公司 | System and method for co-processing waste glass powder and pickling waste liquid |
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