CN106336039A - Method of non-noxious treatment of scrapped silicon dioxide etching solution - Google Patents
Method of non-noxious treatment of scrapped silicon dioxide etching solution Download PDFInfo
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- CN106336039A CN106336039A CN201610850751.1A CN201610850751A CN106336039A CN 106336039 A CN106336039 A CN 106336039A CN 201610850751 A CN201610850751 A CN 201610850751A CN 106336039 A CN106336039 A CN 106336039A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method of completely non-noxious treatment of a scrapped silicon dioxide etching solution. The method adopts a second stage method, and specifically, the primary treatment is to adjust the pH value of waste fluid, add calcium salt to remove fluorine and meanwhile perform air stripping to remove ammonia nitrogen; secondary treatment is to adjust the pH value of filtrate, add calcium hypochlorite, keep the pH value and perform stirring reaction for a certain time, enable ammoniacal nitrogen to be oxidized into harmless nitrogen gas for complete removing, add ferrous salt to remove active chlorine, ensure that all filtered residues enter a cement kiln, so as to be comprehensively utilized, and ensure that secondary filtrate can achieve the primary standard of integrated wastewater discharge standard. Completely non-noxious treatment of the scrapped silicon dioxide etching solution can be realized through the treatment method.
Description
Technical field
The invention belongs to integrated wastewater processing technology field is and in particular to one kind is scrapped at SiO 2 etch liquid pollution-free
Reason method.
Background technology
Wet etching is accurately controlled in the removal amount of thin film and technical process to the loss of raw material relatively because of its technique
Low be widely used in current IC manufacturing field, and the etching solution scrapped contains the fluorine of high concentration and ammoniacal nitrogen to environment
And Pollution of Eco-system Environment is very serious.Cn201010525143a, cn103030234a, cn104961304a, Liu open integrated circuit
Industrial fluoride wastewater treatment technical research and application, the technological improvement of Cheng Xiu silk floss fluoride wastewater treatment technique, the old Calx-sulfur that sets a prairie fire
Sour aluminum method process high-concentration fluorine-containing waste water experimentation is studied just for the processing method of fluoride waste, and does not refer to ammonia state
The process of nitrogen；The high-efficiency air strippings such as the high-concentration ammonia nitrogenous wastewater experimental study such as Huo Ying, Huang Jun and break point chlorination process high ammonia nitrogen and give up
Water is only studied to high-concentration ammonia nitrogenous wastewater；Cn102126799a, cn103011441a are fluorine-containing, the process of nitrogen-containing wastewater its
Fluorine, ammonia-nitrogen content are all not less than a gram level；The fluorine-containing nitrogenous effluent treatment of cn104961304a, cn103936218a, the place being used
Reason method equipment is many, and technological process is long；The photovoltaic wastewater of Zhang Xinlong is processed in experimentation and is combined with reverse osmosiss using materialization
Process the fluorine-containing nitrogenous effluent of photovoltaic, its reverse osmosis membrane need to constantly clean, and processing cost is very high；A kind of ammonium fluoride of cn102659277a
Waste water treatment process, is combined and is processed using ultrafiltration, electrodialysis, nanofiltration, be only suitable for the application of low concentration ammonium fluoride waste water,
Investment and operating cost are all high.
Content of the invention
For solving above-mentioned technical problem, a kind of complete harmless treatment side of SiO 2 etch liquid scrapped of disclosure
Method.Specific technical scheme is as follows:
The present invention relates to a kind of SiO 2 etch liquid processing method scrapped, the SiO 2 etch processing in the method
Liquid is buffer oxide layer etching solution, and main component mixes according to different proportion for hf and nh4f, acid or faintly acid, Oil repellent
For 30g/l, ammonia-nitrogen content is 20g/l.Generally, described its Oil repellent of SiO 2 etch liquid scrapped
20-35g/l, ammonia-nitrogen content is in 15-25g/l.
Specifically, the step that the method includes two stage treatment:
Coagulation is the ph value of adjustment waste liquid, adds calcium salt, and air stripping removes ammonia nitrogen simultaneously, reacts the regular hour,
Most of ammoniacal nitrogen stripping removes, and the ammonia of removing is absorbed with sulfuric acid solution, and absorbing liquid can obtain ammonium sulfate side-product through evaporative crystallization；
Fluorion generates calcium fluoride with calcium binding, and precipitation is filtered.
Two stage treatment adjusts certain ph value for filtrate, plus calcium hypochlorite, keeps this ph value stirring reaction regular hour, makes
Ammoniacal nitrogen is oxidized to innoxious nitrogen and removes completely, plus ferrous salt removes effective chlorine, and the iron ion being oxidized to trivalent can lure again
Lead calcium fluoride crystallization, secondary all filtering residues enter cement kiln comprehensive utilization by precipitation filtration, and secondary filtrate is up to " integrated wastewater is arranged
Put standard " primary standard.Process the complete harmless treatment of SiO 2 etch liquid that can make to scrap through said method.
Specifically, technical scheme is realized by following step:
1) the etching solution Oil repellent that analysis detection is scrapped；
2) add calcium salt and adjust solution ph, after ph value stabilization, stripping reacts the regular hour, makes most of ammoniacal nitrogen
With the removing of ammonia form, fluorine generates calcium fluoride precipitate with calcium binding；
In the case of preferably, above-mentioned steps 2) used by calcium salt can for calcium chloride, Calcium Carbonate, calcium oxide, calcium hydroxide or
Its mixture.The addition of calcium ion is 1.1-1.5 times that all fluorions generate calcium fluoride Theoretical Calculation, most preferably 1.4 times.
Above-mentioned steps 2) concrete operation method be: in the SiO 2 etch liquid scrapped add calcium salt adjust ph value 10-
13, it is most preferably 12.Because if ph≤10, in filtrate, the ammoniacal nitrogen of residual and fluorion are too high, increase follow-up in this method
The difficulty of two stage treatment, if ph >=13, the processing cost of this method will increase.
3) by step 2) slag-water slurry filtering residue and filtrate are isolated with methods such as sucking filtration, filter pressing, centrifugations；Most preferably
Carry out separating using centrifugal separation method.
4) by step 2) ammonia that removes absorbs with sulfuric acid solution, and absorbing liquid carries out evaporative crystallization after scrapping, obtains side-product sulfur
Sour ammonium；Evaporation crystallization equipment may be selected falling film type, rises membrane type, standard vertical-tubes, board-like, forced circulation etc., is energy saving
Most preferably adopt multi-effect evaporator.
5) by step 3) gained filtrate detection ammonia-nitrogen content；Now ammonia-nitrogen content is typically less than 1000mg/l.
6) by step 3) gained filtrate adds mineral acid adjustment ph value, plus calcium hypochlorite, stirring reaction 1 hour, makes ammoniacal nitrogen
Be fully converted into nitrogen remove, then plus ferrous salt remove chlorine residue while increase calcium fluoride sedimentation velocity；
Step 6) described in mineral acid can be hydrochloric acid, sulphuric acid or its mixed liquor；Adjust ph value 8, the lower calcium hypochlorite of this ph value
The best results of oxidation ammoniacal nitrogen.
The effective chlorine of the calcium hypochlorite being used is more than 60%, and addition is calculated as remaining ammonia nitrogen quality after stripping with effective chlorine
7.8-8.5 times, this addition ammoniacal nitrogen energy complete oxidation is nitrogen, and will not produce chlorine derivative；Oxidation time 1 is little
When.Oxidant is done using calcium hypochlorite, both make use of the oxidisability of hypochlorite, the fluorine removal also taking full advantage of calcium ion is made
With,
Step 6) added by ferrous salt be ferrous sulfate, ferrous chloride or its mixture, specifically, described ferrous salt can be single
Solely reaction system is added with solid or suspension or be mixed in proportion with solid or suspension addition reaction system, addition is to form sediment
Powder potassium iodide starch paper is instruction, is become colorless by blueness, eliminates chlorine residue non-oxidative, is oxidized to the iron ion of trivalent again
Inducible calcium fluoride crystallization.
7) by step 6) slag-water slurry filtering residue and filtrate are isolated with methods such as sucking filtration, filter pressing, centrifugations；
The separate mode of slag-water slurry can adopt sucking filtration, filter pressing, centrifugation etc., enters preferably with centrifugal separation method
Row separates.
8) by step 3) and 7) gained filtering residue enter cement kiln comprehensive utilization；Secondary filtrate is up to " integrated wastewater discharge standard "
Primary standard.
Beneficial effect: by the inventive method, the SiO 2 etch liquid scrapped is processed and can thoroughly solve SiO 2 etch
Liquid problem of environmental pollution, this method process is simple, equipment is less, and processing cost is low, can process fluorine and the ammonia of high concentration simultaneously
State nitrogen, recovery side-product is ammonium sulfate, and gained filtering residue all can enter cement kiln comprehensive utilization, turn waste into wealth, prevent secondary pollution,
Secondary filtrate is up to " integrated wastewater discharge standard " primary standard.The SiO 2 etch liquid scrapped can be made to reach completely innoxious
Process, can its pollution problem to environment and ecosystem of effectively solving.
Specific embodiment
Following non-limiting examples can make those of ordinary skill in the art that the present invention is more fully understood, but not with
Any mode limits the present invention.Any those familiar with the art in the technical scope of present disclosure, according to
Technical scheme and its inventive concept carry out equivalent or change and belong to protection category of the present invention.
Embodiment 1～5
Coagulation:
Add the SiO 2 etch liquid 1000ml scrapping in 2000ml three-necked bottle, this waste liquid Oil repellent is 33.5g/l,
Ammonia-nitrogen content is 19.6g/l, adds 20% lime cream to adjust ph value 10-13, if calcium amount not, adds chlorination after ph value stabilization
Calcium makes 1.1-1.5 times that the addition of its calcium is theoretical amount；Be passed through air stripping reaction 1-3 hour, make most of ammoniacal nitrogen with
Ammonia form removes, and fluorine generates calcium fluoride precipitate with calcium binding, and sucking filtration isolates filtering residue and filtrate, the enforcement of coagulation
Condition and treatment effect are as shown in table 1.
The ammonia of above-mentioned removing is absorbed with 10% sulfuric acid solution, and absorbing liquid scraps rear evaporative crystallization, obtains byproduct of ammonium sulfate.
The implementation condition of coagulation and treatment effect in table 1. embodiment 1-5
The filtrate 200ml that coagulation embodiment 3 method is obtained is added in 500ml beaker.Add under stirring
10% sulphuric acid adjusts ph7.5-8, plus effective chlorine is more than 60% calcium hypochlorite stirring reaction 1 hour, and oxidation removes ammonia nitrogen, and chlorine residue adds sulfur
Acid is ferrous to be removed, and addition, with starch potassium iodide paper for instruction, is become colorless by blueness, eliminates chlorine residue non-oxidative.
Table 2 two stage treatment embodiment 1-2 implementation condition and treatment effect
From the point of view for the treatment of effect by embodiment 1～5, the addition that table 1 data display works as calcium is the 1.1-1.5 of theoretical amount
Times, when ph value is more than 10, in filtrate, the content of fluorine drops to below 100mg/l；When the addition of calcium is 1.4 times of theoretical amount, ph
When being worth for 12, Oil repellent in filtrate can drop to 10mg/l；When ph value is 12, stripping reaction 2 is little constantly, and ammonia nitrogen can drop
To 400mg/l about；Coagulation has reached the purpose removing most fluorine and ammoniacal nitrogen.Table 2 data display calcium hypochlorite
During addition 7.8-8.5 times, can effectively remove the ammoniacal nitrogen in filtrate, calcium ion can remove remaining a small amount of fluorine simultaneously, reaches
Discharge primary standard to integrated wastewater；Demonstrate the complete harmless treatment of SiO 2 etch liquid that the method can make to scrap.
Claims (8)
1. a kind of SiO 2 etch liquid processing method scrapped it is characterised in that:
1) calcium salt is added to adjust ph value 10-13 in the SiO 2 etch liquid scrapped, after ph value stabilization, stripping reacts 1-3 hour；
Isolate filtering residue and filtrate；The ammonia of removing is absorbed with sulfuric acid solution, and absorbing liquid carries out evaporative crystallization after scrapping, obtains side-product sulphuric acid
Ammonium；
2) gained filtrate adds mineral acid adjustment ph value 7.5, plus calcium hypochlorite, stirring reaction 1 hour, so that ammoniacal nitrogen is fully converted into
Nitrogen remove, then plus ferrous salt remove chlorine residue while increase calcium fluoride sedimentation velocity；Ferrous salt addition is with starch iodate
Potassium reagent paper is become colorless as indicating by blueness, finally with methods such as sucking filtration, filter pressing, centrifugations, slag-water slurry is isolated filter
Slag and filtrate.
2. method according to claim 1 it is characterised in that: described step 1) used by calcium salt can be calcium chloride, carbonic acid
Calcium, calcium oxide, calcium hydroxide or its mixture.
3. method according to claim 1 it is characterised in that: described step 1) described calcium ion addition be all fluorine
Ion generates 1.1-1.5 times of calcium fluoride theoretical amount.
4. method according to claim 1 it is characterised in that: described step 1) described in isolate the method for filtering residue and filtrate
Selected from sucking filtration, filter pressing, centrifugal separation method.
5. method according to claim 1 it is characterised in that: described step 1) equipment used by described evaporative crystallisation process
For falling film type, rise membrane type, standard vertical-tubes, board-like, forced cyclic type or multi-effect evaporator.
6. method according to claim 1 it is characterised in that: described step 2) described in mineral acid be hydrochloric acid, sulphuric acid or
Its mixed liquor.
7. method according to claim 1 it is characterised in that: described step 2) effective chlorine of calcium hypochlorite that uses is more than
60%, addition is calculated as 7.8-8.5 times of remaining ammonia nitrogen quality after stripping with effective chlorine.
8. method according to claim 1 it is characterised in that: described step 2) in ferrous salt be ferrous sulfate, chlorination
Ferrous iron or its mixture.
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| CN201610850751.1A CN106336039B (en) | 2016-09-26 | 2016-09-26 | One kind scrapping SiO 2 etch liquid pollution-free processing method |
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| CN201610850751.1A CN106336039B (en) | 2016-09-26 | 2016-09-26 | One kind scrapping SiO 2 etch liquid pollution-free processing method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368859A (en) * | 2018-11-15 | 2019-02-22 | 河南利华制药有限公司 | Upper fluorine waste water zero discharge treatment process in steroidal drug production |
| CN112110589A (en) * | 2020-09-27 | 2020-12-22 | 大连东泰产业废弃物处理有限公司 | Harmless treatment method of high-concentration buffered hydrofluoric acid etching waste liquid |
| CN114853223A (en) * | 2022-06-20 | 2022-08-05 | 淄博灵芝化工有限公司 | Method for removing phosphorus and residual chlorine from high-concentration residual chlorine-containing alkaline wastewater |
| CN115477315A (en) * | 2022-10-27 | 2022-12-16 | 无锡中天固废处置有限公司 | Method for preparing potassium fluoride by using buffer oxide etching waste liquid |
| CN117919646A (en) * | 2024-03-20 | 2024-04-26 | 崇义章源钨业股份有限公司 | Method for treating high-fluorine ammonia-containing slag |
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| CN105859028A (en) * | 2016-04-29 | 2016-08-17 | 红板（江西）有限公司 | Process for treating circuit board alkaline etching ammonia-nitrogen wastewater |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368859A (en) * | 2018-11-15 | 2019-02-22 | 河南利华制药有限公司 | Upper fluorine waste water zero discharge treatment process in steroidal drug production |
| CN112110589A (en) * | 2020-09-27 | 2020-12-22 | 大连东泰产业废弃物处理有限公司 | Harmless treatment method of high-concentration buffered hydrofluoric acid etching waste liquid |
| CN112110589B (en) * | 2020-09-27 | 2022-09-09 | 大连东泰产业废弃物处理有限公司 | Harmless treatment method of high-concentration buffer hydrofluoric acid etching waste liquid |
| CN114853223A (en) * | 2022-06-20 | 2022-08-05 | 淄博灵芝化工有限公司 | Method for removing phosphorus and residual chlorine from high-concentration residual chlorine-containing alkaline wastewater |
| CN115477315A (en) * | 2022-10-27 | 2022-12-16 | 无锡中天固废处置有限公司 | Method for preparing potassium fluoride by using buffer oxide etching waste liquid |
| CN115477315B (en) * | 2022-10-27 | 2024-01-30 | 无锡中天固废处置有限公司 | Method for preparing potassium fluoride by utilizing buffer oxide etching waste liquid |
| CN117919646A (en) * | 2024-03-20 | 2024-04-26 | 崇义章源钨业股份有限公司 | Method for treating high-fluorine ammonia-containing slag |
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| CN106336039B (en) | 2019-08-02 |
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