CN109809431A - A kind of method of siliceous, fluorine and ammonium Sewage treatment ammonium acid fluoride, white carbon black co-product ice crystal - Google Patents
A kind of method of siliceous, fluorine and ammonium Sewage treatment ammonium acid fluoride, white carbon black co-product ice crystal Download PDFInfo
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Abstract
The invention discloses the methods of a kind of siliceous, fluorine and ammonium Sewage treatment ammonium acid fluoride, white carbon black co-product ice crystal, the described method comprises the following steps: (1) precipitating reagent, available precipitating S and solution A being added into waste water；(2) it obtains that sodium hydroxide solution adjusting pH=8~12, filtering, available white carbon black and solution B are added in precipitating S in step (1)；(3) substance containing aluminum chemistry is added in the solution B that step (2) obtains, sufficiently reacts, ice crystal, filtrate recycling is obtained by filtration；(4) hydrofluoric acid is added in the solution A that step (1) obtains and adjusts pH=1~6, the available ammonium acid fluoride of condensing crystallizing.Treatment process of the present invention is simple, can simultaneously obtain three kinds of higher ice crystal of value, ammonium acid fluoride and white carbon black products, has good practical value.
Description
Technical field
The present invention relates to technical field of waste water processing, more particularly, to a kind of siliceous, fluorine and ammonium Sewage treatment ammonium acid fluoride,
The method of white carbon black co-product ice crystal.
Background technique
Siliceous, fluorine and ammonium waste water are mainly derived from the industries such as silicon chip etching, photovoltaic industry and glass etching, former etchant water
In mainly fluorine and ammonium, silicon is gradually introduced in treatment process and forms fluosilicic acid.With the rapid development of relevant industries, such waste water
Influence to environment is increasingly severe, and a large amount of discharges of ammonia nitrogen and fluorine ion can all generate very big harm to environment.Work as water body
In ammonia nitrogen it is excessively high, will lead to water eutrophication, and fluorine ion will lead to soil texture variation, therefore such waste water needs are sought
Suitable scheme is looked for be effectively treated.
Such waste water is mainly handled by following several method at present: 1 aeration neutralisation is added using common process
Enter superfluous lime, ammonia nitrogen is aerated and is absorbed under strong basicity, the impurity such as fluorine and silicon form precipitating.This method simple process, but
It is that can generate the secondary waste of a large amount of calcium fluoride sludge, and result in waste of resources.2 membrane process, CN 201210144809.2 are public
A kind for the treatment of process of ammonium fluoride waste water is opened, the process is the following steps are included: ammonium fluoride waste water pre-treatment, at ultrafiltration
Reason, electrodialysis process, nanofiltration processing, when ammonium fluoride content is less than 5ppm in the ammonium fluoride solution handled through nanofiltration, i.e.,
The processing for completing ammonium fluoride waste water recycles ammonium salt in conjunction with condensing crystallizing.This method although avoid ammonia nitrogen aeration removal and
Fluorine precipitating removal, but it is not strong for silicon-containing wastewater applicability, and also the waste strength of general siliceous, fluorine and ammonium is all higher,
It is not applicable to be handled with embrane method.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of siliceous, fluorine and ammonium Sewage treatments
The method of ammonium acid fluoride, white carbon black co-product ice crystal.Treatment process of the present invention is simple, can simultaneously obtain the higher ice crystal of value
Three kinds of stone, ammonium acid fluoride and white carbon black products have good practical value.
Technical scheme is as follows:
A kind of method of siliceous, fluorine and ammonium Sewage treatment ammonium acid fluoride, white carbon black co-product ice crystal, the method includes with
Lower step:
(1) precipitating reagent, available precipitating S and solution A are added into waste water；
(2) it obtains that sodium hydroxide solution adjusting pH=8~12 are added in precipitating S in step (1), filtering is available
White carbon black and solution B；
(3) substance containing aluminum chemistry is added in the solution B that step (2) obtains, sufficiently reacts, ice crystal is obtained by filtration, filters
Liquid recycling；
(4) hydrofluoric acid is added in the solution A that step (1) obtains and adjusts pH=1~6, the available hydrogen fluoride of condensing crystallizing
Ammonium.
Fluorine in wastewater silicic acid described in step (1) can react production precipitating completely with precipitating reagent, without containing the fluorine-containing of silicon
Ammoniated wastewater also should be 0 in the column of protection, the i.e. amount of addition precipitating reagent.
Precipitating reagent described in step (1) includes but is not limited to potassium carbonate, potassium hydroxide, sodium carbonate, one in sodium hydroxide
Kind is a variety of.
Precipitating S described in step (2) includes but is not limited to one of prodan, potassium fluosilicate or a variety of.
Substance containing aluminum chemistry described in step (3) includes but is not limited to one of sodium aluminate, aluminium hydroxide or a variety of.
The mode of condensing crystallizing described in step (4) is membrane technology or evaporation and concentration.
The sodium carbonate is technical grade purity.
The aluminum fluoride is technical grade product.
The ammonium hydrogen carbonate is technical grade purity.
The present invention is beneficial to be had the technical effect that
The invention discloses the methods of a kind of siliceous, fluorine and ammonium Sewage treatment ammonium acid fluoride, white carbon black co-product ice crystal, originally
Siliceous, fluorine and ammonium waste water by precipitating, filtering, reaction, neutralization, concentration, cooling, crystallization, drying, are respectively obtained ice crystal by method
Stone, silica and ammonium acid fluoride product can make the waste water rich in silicon, fluorine and ammonium realize recycling.The present invention handles work
Skill is simple, can simultaneously obtain three kinds of higher ice crystal of value, ammonium acid fluoride and white carbon black products, has good practical valence
Value.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1
The 1000mL of certain semiconductor producer production line siliceous (fluorine silicon 2%), fluorine and ammonium waste water are taken, ammonium fluoride 2% is contained, is added
5g sodium hydroxide, available 20g prodan and 1000mL ammonium fluoride solution；By 10% sodium hydroxide of 20g prodan
Solution is dissolved, and is adjusted pH=8, white carbon black 7.4g is obtained by filtration, the rate of recovery 95% obtains solution Fluorinse
100mL；Aluminum fluoride 15g is added in solution B, sufficiently reacts, filters available ice crystal 25g, the rate of recovery 99%；By solution
A is added ammonium hydrogen carbonate and adjusts pH=1, the available ammonium acid fluoride 20g of single-action stainless steel equipment condensing crystallizing, and the rate of recovery is
99%.
Embodiment 2
The 1000mL of certain semiconductor producer production line siliceous (fluorine silicon 2%), fluorine and ammonium waste water are taken, ammonium fluoride 8% is contained, is added
10g potassium carbonate, available 26g potassium fluosilicate, the rate of recovery 99%, 1000mL ammonium fluoride solution；26g potassium fluosilicate is used
10% potassium hydroxide solution is dissolved, and adjusts pH=10, white carbon black 7.5g is obtained by filtration, the rate of recovery 96% is fluorinated
Potassium solution 100mL；Aluminum sulfate 25g, sodium sulphate 25g are added in solution B, sufficiently reacts, filters available ice crystal 24g, returns
Yield is 98%；Hydrofluoric acid is added in ammonium fluoride solution and adjusts pH=3, the two effect available hydrogen fluoride of graphite equipment condensing crystallizing
Ammonium 78, the rate of recovery 99%.
Embodiment 3
The 1000mL of certain semiconductor producer production line siliceous (fluorine silicon 2%), fluorine and ammonium waste water are taken, ammonium fluoride 8% is contained, add
Enter 13g sodium carbonate, available 20g prodan and 1000mL ammonium fluoride solution；By 10% sodium hydroxide of 20g potassium fluosilicate
Solution is dissolved, and is adjusted pH=12, white carbon black 7.6g is obtained by filtration, the rate of recovery 97% obtains Fluorinse 100mL；
Sodium aluminate 25g is added in solution B, sufficiently reacts, filters available ice crystal 25g, the rate of recovery 99%；By ammonium fluoride solution
Hydrofluoric acid is added and adjusts pH=6, the available ammonium acid fluoride 75g of membrane distillation concentration crystallisation by cooling, the rate of recovery 94%.
Claims (6)
1. a kind of method of siliceous, fluorine and ammonium Sewage treatment ammonium acid fluoride, white carbon black co-product ice crystal, which is characterized in that described
Method the following steps are included:
(1) precipitating reagent, available precipitating S and solution A are added into waste water；
(2) it obtains that sodium hydroxide solution adjusting pH=8~12, filtering, available hard charcoal are added in precipitating S in step (1)
Black and solution B；
(3) substance containing aluminum chemistry is added in the solution B that step (2) obtains, sufficiently reacts, ice crystal is obtained by filtration, filtrate is returned
It receives；
(4) hydrofluoric acid is added in the solution A that step (1) obtains and adjusts pH=1~6, the available ammonium acid fluoride of condensing crystallizing.
2. the method according to claim 1, wherein fluorine in wastewater silicic acid described in step (1) can be with precipitating
Production precipitating is reacted in agent completely, and the fluorine-containing ammoniated wastewater without containing silicon also should be 0 in the column of protection, the i.e. amount of addition precipitating reagent.
3. the method according to claim 1, wherein precipitating reagent described in step (1) includes but is not limited to carbonic acid
One of potassium, potassium hydroxide, sodium carbonate, sodium hydroxide are a variety of.
4. the method according to claim 1, wherein precipitating S described in step (2) includes but is not limited to fluosilicic acid
One of sodium, potassium fluosilicate are a variety of.
5. the method according to claim 1, wherein substance containing aluminum chemistry described in step (3) includes but unlimited
In one of sodium aluminate, aluminium hydroxide or a variety of.
6. the method according to claim 1, wherein the mode of condensing crystallizing described in step (4) is membrane technology
Or it is concentrated by evaporation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885147A (en) * | 2019-12-05 | 2020-03-17 | 南京大学 | Ion exchange defluorination method for efficiently complexing fluorine-containing wastewater |
| CN112811555A (en) * | 2021-02-05 | 2021-05-18 | 盛隆资源再生（无锡）有限公司 | Recycling method of fluorine-containing sulfuric acid waste liquid |
| CN116495751A (en) * | 2023-06-27 | 2023-07-28 | 盛隆资源再生（无锡）有限公司 | Method for co-producing potassium fluoride and ammonium fluosilicate from silicon-containing fluorine-containing ammonia-containing acidic etching solution |
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| CN102745837A (en) * | 2012-07-18 | 2012-10-24 | 上海交通大学 | Method for treating and recycling glass thinning and etching waste liquor |
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| CN102745837A (en) * | 2012-07-18 | 2012-10-24 | 上海交通大学 | Method for treating and recycling glass thinning and etching waste liquor |
| CN104973580A (en) * | 2015-07-02 | 2015-10-14 | 苏州晶洲装备科技有限公司 | Collecting and recycling method of polycrystalline silicon texturing etching waste liquid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885147A (en) * | 2019-12-05 | 2020-03-17 | 南京大学 | Ion exchange defluorination method for efficiently complexing fluorine-containing wastewater |
| CN110885147B (en) * | 2019-12-05 | 2021-11-26 | 南京大学 | Ion exchange defluorination method for efficiently complexing fluorine-containing wastewater |
| CN112811555A (en) * | 2021-02-05 | 2021-05-18 | 盛隆资源再生（无锡）有限公司 | Recycling method of fluorine-containing sulfuric acid waste liquid |
| CN116495751A (en) * | 2023-06-27 | 2023-07-28 | 盛隆资源再生（无锡）有限公司 | Method for co-producing potassium fluoride and ammonium fluosilicate from silicon-containing fluorine-containing ammonia-containing acidic etching solution |
| CN116495751B (en) * | 2023-06-27 | 2023-10-03 | 盛隆资源再生（无锡）有限公司 | Method for co-producing potassium fluoride and ammonium fluosilicate from silicon-containing fluorine-containing ammonia-containing acidic etching solution |
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