CN107215996A - A kind of recycling treatment system, processing method and the application of high concentration sodium salt waste water - Google Patents
A kind of recycling treatment system, processing method and the application of high concentration sodium salt waste water Download PDFInfo
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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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/44—Concentration
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/46—Purification; Separation ; Stabilisation
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/42—Concentration; Dehydration
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
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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
- C02F2101/101—Sulfur compounds
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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
- C02F2101/105—Phosphorus compounds
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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
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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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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Abstract
The invention discloses a kind of recycling treatment system of high concentration sodium salt waste water, the system includes acid-alkali regeneration device, acid-alkali regeneration device lye export is connected with alkali concentration unit, acid solution is exported to be connected with sour concentration unit, raffinate outlet is connected with electrodialysis or counter-infiltration, obtained concentrated acid concentrated base is reclaimed, raffinate concentrated water Returning utilization, and final residue water can also reuse；The processing system that the present invention is provided is realized sodium salt and reclaimed in the form of concentrated acid concentrated base, and remaining water realizes reuse, finally realizes zero-emission, and equipment is simple, flexible controllable, the double benefit with environmental economy.
Description
Technical field
The present invention relates to sewage advanced treatment field, more particularly to a kind of recycling treatment system of high concentration sodium salt waste water
System, processing method and application.
Background technology
At present, the high-concentration waste water containing sodium salt obtained in industrial production is used at directly discharge or evaporative crystallization method mostly
Reason, sodium salt is reclaimed by evaporative crystallization method, and not only energy consumption is big, and the sodium salt reclamation rate reclaimed is low, cheap；As directly arranged
Salt, water resource waste can not only be caused by putting, and environment can be damaged.
In summary, inventor concentrates on studies to choose carries out acid-alkali regeneration using bipolar membrane electrodialysis method, and further right
Soda acid carries out concentrate, can not only be reclaimed salt in the form of alkali lye and high concentration acid solution, and can realize the zero-emission of process water
Put, the double benefit with environment-economy, effect is notable.
The content of the invention
For above-mentioned technical problem, the invention provides a kind of recycling treatment system of high concentration sodium salt waste water, processing
Method and application, the system equipment are simple, workable, flexibly controllable, can handle the waste water that sodium salt concentration is 5% ~ 50%,
With good market prospects.
In order to solve the above problems, the present invention uses following technical scheme：
A kind of recycling treatment system of high concentration sodium salt waste water, the system includes acid-alkali regeneration device, the acid-alkali regeneration
Device lye export is connected with alkali concentration unit, and acid solution outlet is connected with sour concentration unit, so as to realize the recovery of salt.
The acid-alkali regeneration device raffinate outlet connection enrichment facility, obtained fresh water reuse, concentrated water returns to acid-alkali regeneration
Device.
The acid-alkali regeneration device is preferably bipolar membrane electrodialysis device.
The alkali concentration unit is one or more combinations in evaporation and concentration, membrane distillation, electrodialysis or reverse osmosis unit.
The sour concentration unit is that evaporation and concentration, rectifying, film absorption, membrane distillation, absorption method or resin block in subtraction unit
One or more.
The enrichment facility is preferably electrodialysis or reverse osmosis unit.
A kind of processing method using above-mentioned processing system, the waste water enters bipolar membrane electrodialysis and regenerated after pretreatment
Dilute alkaline soln and dilute acid soln are obtained, the dilute alkaline soln liquid enters alkali concentration unit, and the dilute acid soln enters sour concentrate dress
Put.
The high-concentration alkali liquor that the dilute alkaline soln is obtained after alkali concentration unit is reclaimed, remaining Water circulation；The diluted acid is molten
The concentrated acid that liquid is obtained after sour concentration unit is reclaimed, remaining Water circulation.
The concentrated water that the bipolar membrane electrodialysis raffinate is obtained after electrodialysis or reverse-osmosis treated returns to bipolar membrane electrodialysis
Water inlet, obtained fresh water reuse.
A kind of purposes using above-mentioned processing system, it is used for high concentration sodium salt field of waste water treatment.
Compared with prior art, the invention has the advantages that：
1st, the invention discloses a kind of recycling treatment system of high concentration sodium salt waste water, using the system processing method and
The systematic difference；
2nd, the present invention carries out acid-alkali regeneration by preferred bipolar membrane electrodialysis, sodium salt is finally realized back in the form of concentrated acid concentrated base
Receive, and realize the zero-emission of whole process system process water, the double benefit with environment-economy；
3rd, processing system equipment of the present invention is simple, flexible controllable, simple to operate, high treating effect, can effectively handle 5% ~ 50%
Sodium salt waste water.
Brief description of the drawings
Fig. 1 is the recycling treatment system process chart of high concentration sodium salt waste water of the present invention.
Embodiment
Further illustrate technical scheme with reference to the accompanying drawings and examples:
As shown in figure 1, a kind of recycling treatment system of high concentration sodium salt waste water, the system includes acid-alkali regeneration device, soda acid
Regenerating unit lye export is connected with alkali concentration unit, and acid solution outlet is connected with sour concentration unit, so as to realize the recovery of salt；
Acid-alkali regeneration device raffinate outlet connection enrichment facility, obtained fresh water reuse, concentrated water returns to acid-alkali regeneration device.
Wherein, acid-alkali regeneration device is preferably bipolar membrane electrodialysis device, alkali concentration unit be evaporation and concentration, membrane distillation,
One or more combinations in electrodialysis or reverse osmosis unit；Sour concentration unit be evaporation and concentration, rectifying, film absorption, membrane distillation,
One or more in absorption method or resin retardance subtraction unit；Enrichment facility is preferably electrodialysis or reverse osmosis unit.
In actual applications, first high concentration sodium salt waste water is pre-processed, and soda acid is carried out subsequently into bipolar membrane electrodialysis
Regeneration, the high alkali liquid that sig water is concentrated to give through alkali concentration unit is reclaimed, the concentrated acid that pickle is concentrated to give through sour concentration unit
Liquid is reclaimed, and the remaining water finally produced can be with reuse；
At the same time, the raffinate of bipolar membrane electrodialysis water inlet can further be concentrated to give concentrated water through electrodialysis or counter-infiltration and return
Return bipolar membrane electrodialysis and enter Water circulation, fresh water reuse finally not only realizes soda acid recovery and also achieves zero-emission, effect is good
It is good.
Embodiment 1
The sodium sulfate wastewater of certain enterprise production, pH=8, sodium sulphate content is 10%.
Step（1）：Above-mentioned sodium sulfate wastewater first adds sulphur acid for adjusting pH=7；
Step（2）：Step（1）Water outlet enters bipolar membrane electrodialysis system acid-alkali regeneration through cartridge filter, obtains 6% alkali lye
With 8% sulfuric acid.Residual brine concentration is 0.5%.
Step（3）：Step（2）6% obtained alkali lye enters evaporation concentration system concentrate, and it is molten that recovery obtains 30% sodium hydroxide
Liquid, evaporation condensed water is back to technique.
Step（4）：Step（2）8% obtained sulfuric acid is concentrated into evaporator, and recovery obtains 80% sulfuric acid, recycling condensing water
In technique.
Step（5）：Step（2）0.5% obtained low concentration salt solution is concentrated into counter-infiltration system, obtained concentrated water sulfuric acid
Na concn is 8%, return to step（2）；Fresh water sodium sulfate concentration is 0.01%, is back to technique.
Embodiment 2
The sodium chloride waste water of certain enterprise production, pH=4, sodium chloride content is 20%, chlorine residue 25mg/L.
Step（1）：Above-mentioned ammonium chloride waste-water first removes chlorine residue, is then hydrogenated with sodium oxide molybdena regulation pH=7；
Step（2）：Step（1）Water outlet enters bipolar membrane electrodialysis system acid-alkali regeneration through cartridge filter, obtains 10% hydrogen-oxygen
Change sodium and 12% hydrochloric acid.Residual brine sodium chloride concentration is 3%.
Step（3）：Step（2）10% obtained sodium hydroxide enters membrane distillation system concentrate, and recovery obtains 25% hydrogen-oxygen
Change sodium solution, recycling condensing water is in technique.
Step（4）：Step（2）12% obtained hydrochloric acid enters salt distillation system, and added salt is divided into calcium chloride, rectifying column
Recovered overhead obtains 30% hydrochloric acid, tower reactor effluent reuse.
Step（5）：Step（2）3% obtained low concentration salt solution is concentrated into electrodialysis system, obtained concentrated water sodium chloride
Concentration is 16%, return to step（2）；Fresh water sodium chloride concentration is 0.02%, is back to technique.
Embodiment 3
The sodium nitrate waste water of certain enterprise production, pH=7, nitric acid sodium content is 15%, oily 10mg/L.
Step（1）：The first Adsorption of above-mentioned sodium nitrate waste water is all oily；
Step（2）：Step（1）Water outlet enters bipolar membrane electrodialysis system acid-alkali regeneration through cartridge filter, obtains 9% hydrogen-oxygen
Change sodium and 9% nitric acid.Residual brine sodium nitrate concentration is 1%.
Step（3）：Step（2）9% obtained sodium hydroxide enters electrodialysis system concentrate, and recovery obtains 20% sodium hydroxide
Solution, fresh water naoh concentration is 0.05%, is back to technique.
Step（4）：Step（2）9% obtained nitric acid enters resin and blocks bed concentrate, and recovery obtains 20% nitric acid, remaining water
Total nitrogen ＜ 10mg/L, are back to technique.
Step（5）：Step（2）1% obtained low concentration salt solution is concentrated into electrodialysis system, obtained concentrated water sodium nitrate
Concentration is 14%, return to step（2）；Fresh water sodium nitrate concentration is 0.01%, is back to technique.
Embodiment 4
The sodium carbonate waste water of certain enterprise production, pH=7, carbonate content is 2%, suspension 20mg/L.
Step（1）：Above-mentioned sodium nitrate waste water filtering removes oil removal；
Step（2）：Step（1）Water outlet enters bipolar membrane electrodialysis system acid-alkali regeneration through cartridge filter, obtains 1% hydrogen-oxygen
Change sodium solution and 4% carbonate aqueous solution.Residual brine concentration of sodium carbonate is 0.7%.
Step（3）：Step（2）1% obtained sodium hydroxide enters counter-infiltration system concentrate, and recovery obtains 15% hydroxide
Sodium solution, fresh water is back to technique.
Step（4）：Step（2）4% obtained carbon acid solution enters membrane absorption system and separates carbon dioxide, is inhaled with chilled water
Receipts obtain 10% carbonate aqueous solution, and remaining water total carbon ＜ 5mg/L are back to technique.
Step（5）：Step（2）0.7% obtained low concentration salt solution is concentrated into counter-infiltration system, obtained concentrated water carbonic acid
Na concn is 6%, return to step（2）；Fresh water concentration of sodium carbonate is 0.005%, is back to technique.
Embodiment 5
The sodium phosphate waste water of certain enterprise production, pH=8, phosphoric acid sodium content is 20%, suspension 20mg/L.
Step（1）：The first filter and remove suspended substances of above-mentioned sodium phosphate waste water, it is 7 then to add phosphorus acid for adjusting pH；
Step（2）：Step（1）Water outlet enters bipolar membrane electrodialysis system acid-alkali regeneration through cartridge filter, obtains 10% hydrogen-oxygen
Change sodium solution and 12% phosphate aqueous solution.Residual brine phosphoric acid na concn is 4%.
Step（3）：Step（2）Enter evaporation concentration system concentrate after obtained 10% sodium hydroxide preheating, recovery is obtained
30% sodium hydroxide, evaporation condensed water is back to technique.
Step（4）：Step（2）12% obtained phosphoric acid solution enters membrane distillation system concentrate, obtains 80% phosphoric acid solution,
Recycling condensing water is in technique.
Step（5）：Step（2）4% obtained low concentration salt solution is concentrated into electrodialysis system, obtained concentrated water sodium phosphate
Concentration is 10%, return to step（2）；Fresh water total phosphorus ＜ 10mg/L, are back to technique.
Embodiment 6
The sodium carbonate waste water of certain enterprise production, pH=7, carbonate content is 8%, suspension 20mg/L.
Step（1）：Above-mentioned sodium carbonate waste water filtering removes oil removal；
Step（2）：Step（1）Water outlet enters bipolar membrane electrodialysis system acid-alkali regeneration through cartridge filter, obtains 6% hydrogen-oxygen
Change sodium and 4% carbonate aqueous solution.Residual brine concentration of sodium carbonate is 1%.
Step（3）：Step（2）6% obtained sodium hydroxide obtains 30% hydroxide into the processing of membrane distillation system, recovery
Sodium, recycling condensing water is in technique.
Step（4）：Step（2）4% obtained carbon acid solution adsorbing separation carbon dioxide, carbon dioxide de is attached with freezing
Water absorption obtains 8% carbonate aqueous solution, and remaining water total carbon ＜ 5mg/L are back to technique.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although reference
The present invention is described in detail for preferred embodiment, it will be understood by those within the art that, can be to the present invention
Technical scheme modify or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, it all should cover
Among the scope of the claims of the present invention.
Claims (10)
1. a kind of recycling treatment system of high concentration sodium salt waste water, it is characterised in that the system includes acid-alkali regeneration device,
The acid-alkali regeneration device lye export is connected with alkali concentration unit, and acid solution outlet is connected with sour concentration unit, so as to realize
The recovery of salt.
2. processing system as claimed in claim 1, it is characterised in that the acid-alkali regeneration device raffinate outlet connection concentration dress
Put, obtained fresh water reuse, concentrated water returns to acid-alkali regeneration device.
3. processing system as claimed in claim 1 or 2, it is characterised in that the acid-alkali regeneration device is preferably Bipolar Membrane electricity
Electrodialysis apparatus.
4. processing system as claimed in claim 3, it is characterised in that the alkali concentration unit is evaporation and concentration, membrane distillation, electricity
One or more combinations in dialysis or reverse osmosis unit.
5. processing system as claimed in claim 4, it is characterised in that the sour concentration unit is evaporation and concentration, rectifying, film suction
One or more in receipts, membrane distillation, absorption method or resin retardance subtraction unit.
6. processing system as claimed in claim 5, it is characterised in that the enrichment facility is preferably electrodialysis or counter-infiltration dress
Put.
7. a kind of processing method using the processing system as described in any claim in claim 1-6, it is characterised in that institute
State waste water and obtain dilute alkaline soln and dilute acid soln into bipolar membrane electrodialysis regeneration after pretreatment, the dilute alkaline soln liquid enters
Alkali concentration unit, the dilute acid soln enters sour concentration unit.
8. processing method as claimed in claim 7, it is characterised in that the height that the dilute alkaline soln is obtained after alkali concentration unit
Concentration recycle of alkali liquor, remaining Water circulation；The concentrated acid that the dilute acid soln is obtained after sour concentration unit is reclaimed, remaining Water circulation.
9. processing method as claimed in claim 8, it is characterised in that the bipolar membrane electrodialysis raffinate is through electrodialysis or reverse osmosis
The concentrated water obtained thoroughly after processing returns to bipolar membrane electrodialysis water inlet, obtained fresh water reuse.
10. the purposes of processing system as described in any claim in a kind of 1-6 such as claim, it is used for high concentration sodium salt waste water
Process field.
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Cited By (5)
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| CN108911250A (en) * | 2018-08-01 | 2018-11-30 | 苏州艾吉克膜科技有限公司 | The reclamation set of ammonia-containing water and the reclamation set technique of ammonia-containing water |
| CN109133446A (en) * | 2018-11-06 | 2019-01-04 | 宜宾海丝特纤维有限责任公司 | A kind of on-line control system and method for viscose glue waste liquid |
| CN109761415A (en) * | 2019-02-19 | 2019-05-17 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment process of cobalt deposition with ammonium bicarbonate waste water |
| WO2021144042A1 (en) | 2020-01-15 | 2021-07-22 | Shell Internationale Research Maatschappij B.V. | Water treatment process |
| WO2022143014A1 (en) * | 2020-12-29 | 2022-07-07 | 中海油天津化工研究设计院有限公司 | Resourceful treatment system and method for sodium nitrate wastewater |
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