CN105036424A - Recycling wastewater desalination purification method and application thereof - Google Patents
Recycling wastewater desalination purification method and application thereof Download PDFInfo
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Abstract
The invention discloses a recycling wastewater desalination purification method and application thereof. The purification method includes the following steps that 1, salt-containing organic wastewater is treated through a bipolar membrane, and a water solution containing organic matter, an acid solution and an alkaline solution are obtained; 2, wet oxidation is performed on the solution containing the organic matter under the conditions that the pH ranges from 2 to 12, the pressure ranges from 2 MPa to 8 MPa, and the temperature ranges from 180 DEG C to 300 DEG C, and treating liquid is obtained; 3, aftertreatment is performed on the treating liquid, and water is obtained. The bipolar membrane is used for filtering the salt-containing organic wastewater in advance before treatment. By means of the method for treating the salt-containing organic wastewater through the bipolar membrane and wet oxidation, the COD value of wastewater can be significantly reduced, and meanwhile matter in the wastewater can be effectively recycled.
Description
Technical field
The present invention relates to technical field of waste water processing, be specifically related to a kind of waste water desalination purifying method and application thereof of resource utilization.
Background technology
In chemical process, inevitably producing many salt-containing organic wastewaters, as H acid waste water, T acid waste water, J acid waste water, DSD acid waste water etc., in order to meet the demand of protection of the environment, needing to process these waste water, to reach emission standard.
Such as: the organic pollutants that mainly contains in H acid waste water is naphthalene and naphthalene derivative, and host inorganic thing is sodium sulfate and ammonium salt, and compares other containing the organic waste water of naphthalene system, has its singularity:
(1) pollutant component is complicated, and concentration is high, the H-acid mother liquor of discharging in process of production, containing a large amount of naphthalene derivative, COD up to several ten thousand mg/L, complicated component;
(2) acid strong, pH is greatly between 1 ~ 2;
(3) colourity is dark, and about 1 × 10
5left and right, general in pale brown to chocolate;
(4) toxicity is large, and H acid belongs to condensed-nuclei aromatics, has strong bio-toxicity, if the not treated direct discharge of waste water, by serious environment pollution, also has very large harm to human body;
(5) not readily biodegradable, due to the conjugatedπbond of the delocalization that naphthalene nucleus is made up of 10 carbon atoms, structure quite stable, is difficult to degraded.
T acid producing waste water all belongs to difficult waste water from dyestuff, and waste water COD is respectively at about 70000mg/L, and colourity is dark, complicated component, toxicity are large, saltiness is high, acidity is strong, directly can not carry out biochemical treatment.
The mode of existing process trade effluent is varied, is reduced the pollutant load in waste water by various physical chemistry and biological means, and such as, the treatment process of existing H acid segregation waste water is: first, extracts H acid segregation waste water; Then, carry out concentrated salt steaming, the sodium sulfate obtained does fixed-end forces or reuse.Due to the excess production capacity of sodium sulfate, and the cost that concentrated salt steams is high, the sodium sulfate salt inferior quality of acquisition, and range of application is narrow.
The segregation workshop section of H acid production process of the prior art can produce a large amount of waste water, containing a large amount of sodium sulfate in these waste water, waste water adopts Bipolar Membrane to process after filtering, sulfuric acid (i.e. acidic solution) and sodium hydroxide solution (i.e. basic solution) can be obtained, sodium hydroxide solution can be used for the denitrification process of nitrated workshop section, or for alkali fusion after concentrating.Sulphuric acid soln can be used to preparation end water.
T acid segregation produce waste water successively after filtration with Bipolar Membrane process, obtain sulfuric acid and ammoniacal liquor, sulfuric acid and ammoniacal liquor are back in industrial production.At sulfuric acid and ammoniacal liquor when carrying out reuse, can be further processed it according to specific needs, to reach the requirement of recycling.As concentrated sulfuric acid and ammoniacal liquor, can distinguish reuse to H acid segregation workshop section and in and workshop section.
The present invention compared with prior art, has following beneficial effect:
(1) treatment process provided by the invention significantly can reduce the COD value in waste water, and the clearance of COD is more than 96%;
(2) treatment process provided by the invention adopts Bipolar Membrane process to waste water, in the bronsted lowry acids and bases bronsted lowry reuse obtained to industrial corresponding workshop section, improves the utilization ratio of raw material.
(3) treatment process provided by the invention is suitable for continuous prodution, is easy to industrially apply.
Summary of the invention
The invention provides a kind of waste water desalination purifying method of resource utilization, significantly can reduce the COD value of waste water, the material in waste water effectively be recycled simultaneously.
A waste water desalination purifying method for resource utilization, comprises the following steps:
(1) utilize Bipolar Membrane to process salt-containing organic wastewater, obtain containing the organic aqueous solution, and acidic solution and basic solution;
(2) in pH=2 ~ 12, pressure is 2 ~ 8MPa, and temperature is under the condition of 180 ~ 300 DEG C, carries out wet oxidation, obtain treatment solution to containing organic solution;
(3) aftertreatment is carried out to treatment solution and obtain water outlet.
A small amount of acid or alkali can be comprised in salt-containing organic wastewater of the present invention, method provided by the invention is applicable to organic brine waste of homogeneous phase, be particularly suitable for the process of factory effluent of naphthene sulfonic acid class, heterocyclic (such as indoles) product, such as: H acid, sour, TOBIAS ACID 97MIN.& 98MIN., the J acid of T, Sulpho Tobias Acid, K are sour, the waste water produced in the production processes such as γ acid, during for H acid segregation waste water, the clearance of COD can reach more than 95%.
Method provided by the invention can adopt industrial continuous prodution, and namely salt-containing organic wastewater experiences the treating processes of step (1) ~ step (3) successively continuously, obtains standard compliant process water.
Bipolar Membrane issues unboiled water at electric field action and dissociates, and produces H
+and OH
-ion, and bipolar membrane electrodialysis technology is compound in common electrodialysis by this specific function, thus the production/regeneration of instant acid/alkali can be realized, or acidifying and/or alkalization.If be applied in salt-containing organic wastewater by bipolar membrane electrodialysis technology, not only can make waste water desalination, and the bronsted lowry acids and bases bronsted lowry generated can be back in products production or waste water subsequent disposal.
Method provided by the invention, first trade effluent (i.e. the organic waste water of saliferous) is reclaimed by Bipolar membrane water splitting and obtain acidic solution and basic solution, organic liquid waste after process is through wet oxidation, be small molecules by organic matter degradation, then through aftertreatment, obtain clean pure water, complete the process of waste water.
Wet oxidation is the efficient oxidation technology under a kind of High Temperature High Pressure, applied range and processing efficiency is high, larger molecular organics in waste water can be decomposed and be oxidized to the removal further such as small molecules organic carboxyl acid, alcohols, amine, or carbonic acid gas, sulfurous gas, ammonia, nitrogen etc. are got rid of or absorb.But inorganic salts (such as nitrate, vitriol, halide salt etc.) in waste water can produce corrosion phenomenon to wet oxidation reaction still, reduce reactor work-ing life, improve running cost.
First waste water is carried out desalination by Bipolar Membrane, not only reduces the corrosion of salt to wet oxidation reaction still, reduce costs, also can prepare the clean bronsted lowry acids and bases bronsted lowry that application is more extensive, value is larger.
The present invention have studied composition and the characteristic of salt-containing organic wastewater, analyze the pros and cons of existing treatment process, adopt the combination of bipolar membrane electrodialysis technology and Wet Oxidation Process and other treatment technologies, not only reclaimed salt, the COD value in waste water can also have been reduced greatly.
As preferably, filter in advance before utilizing Bipolar Membrane to process salt-containing organic wastewater.
Before salt-containing organic wastewater enters Bipolar Membrane system, first filter, to remove the solid matter such as suspended substance and iron, calcium, magnesium.
As preferably, in step (1), the treatment condition of Bipolar Membrane are: the voltage <2.5V of individual film, current density is 100 ~ 600A/m
2, temperature is 1 ~ 40 DEG C.
Film in bipolar membrane electrodialysis system mainly contains cavity block, anode membrane, Bipolar Membrane., when running into zwitterion film in transition process, there is selectivity and pass through in the salt in salt-containing organic wastewater and sour or alkali directional migration under the effect of electric field.When running into anode membrane, positively charged ion passes through, and negatively charged ion is trapped; When running into cavity block in like manner; When running into Bipolar Membrane, the ion (H of the band charges of different polarity discharged with film table
+or OH
-) combine, generate acid or alkali.Under electric field action, the ion in waste water all moves away from waste water, with H
+or OH
-in conjunction with generation soda acid, fully recycled the salt in waste water, in the waste water after process, salts contg is lower, little to the corrosion of wet oxidation reaction still.
The object of wet oxidation is the organic matter degradation in solution to be small molecules, reduce COD value, because the condition of wet oxidation is more harsh, long-time use, inevitably equipment is caused damage, in order to take into account the effect of wet oxidation, preferably, in step (2), the time of wet oxidation is 2 ~ 6h.
Further preferably, the pH of wet oxidation is 4 ~ 10, and pressure is 5 ~ 8MPa, and temperature is 200 ~ 280 DEG C, and the reaction times is 2 ~ 4h.Preferred again, the pH of wet oxidation is 6 ~ 10, and pressure is 5 ~ 7MPa, and temperature is 200 ~ 250 DEG C, and the reaction times is 2 ~ 4h.
After wet oxidation, COD value significantly reduces, and urges obtaining treatment solution and carrying out aftertreatment, and described aftertreatment is flocculation and/or decolouring.If decolouring is selected in aftertreatment, preferably, described discoloring agent is one or more in gac, diatomite, aluminum oxide, molecular sieve.。
As preferably, pre-treatment is carried out to the waste water before wet oxidation.Pre-treatment adopts light electrolysis and/or diazonium.Nitrose material can be reduced into amine by light electrolysis, and nitrite and amine react and can generate diazonium product, amine and the easier wet oxidation of diazonium product, and the small molecules that oxidation generates is ammonia, ammonium salt or nitrogen, safer, easily remove.
As preferably, flocculate after light electrolysis, or flocculate after wet oxidation.
As preferably, pre-treatment is carried out before bipolar membrane electrodialysis process, or after bipolar membrane electrodialysis process.When pre-micro-electrolysis disposal carries out before bipolar membrane electrodialysis process, have to pass through after flocculation filtration deironing after Bipolar Membrane.
Process after wet oxidation is aftertreatment, and this aftertreatment is flocculation and/or decolouring.
According to sorbent material decolouring, the add-on of sorbent material is 0.05 ~ 0.5% for the treatment of solution quality.Before adding sorbent material, pH value is adjusted to 6 ~ 8.
According to treatment process of the present invention, can improve the production technique of H acid and other products, illustrate for H acid below
H acid production process after improvement is: refined naphthalene successively through sulfonation, nitrated, neutralization, reduction, T acid segregation, alkali fusion, H acid emanate prepare H acid, H acid segregation produce waste water successively after filtration with Bipolar Membrane process, obtain sulfuric acid and sodium hydroxide, this sulfuric acid and sodium hydroxide are back in industrial production.Such as, by sulfuric acid reuse to H acid segregation workshop section, sodium hydroxide reuse is to alkaline melt workshop section and/or nitrated workshop section.
After adopting Bipolar Membrane process, obtain acidic solution and basic solution, specific to H acid segregation waste water, obtain sulfuric acid and aqueous sodium hydroxide solution.Sulphuric acid soln can be used to prepare the end water dilute sulphuric acid of the end water used to be massfraction be 15-20% (during the H acid segregation).Sodium hydroxide solution can be used for the denitrification process of nitrated workshop section, or for alkali fusion, (nitrosyl-sulfuric acid produced in nitrifying process produces a large amount of oxynitride tail gas after adding water after concentrated, utilize the alkaline solution be recovered to absorb this tail gas, the nitrite solution of generation can be used for doazo reaction).
Embodiment
Embodiment 1
H acid waste water, in black, COD=26030mg/L, pH=2.
(1) H acid waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium;
(2) Bipolar Membrane process: utilize Bipolar Membrane process filtrate, obtains basic solution and massfraction is the sulfuric acid of 10%, and in basic solution, the massfraction of sodium hydroxide is 4%, and the massfraction of ammonia is 4%.The condition of Bipolar Membrane is: individual membrane voltage is 2.0V, and current density is 600A/m
2, temperature is 30 DEG C, and the treatment time is 120min.
(3) wet oxidation: by the pH regulator to 7 containing organic solution obtained after Bipolar Membrane process, then squeeze in wet oxidation still, be warming up to 250 DEG C, pressure 6MPa, lower the temperature after passing into atmospheric oxidation 2h.
Record out still waste water and show orange-yellow, pH=4.5, COD=2083mg/L, NH
3-N=164.2mg/L.
(4) adsorb: the still waste water that goes out of step (3) is adjusted to neutral pH=7, adding massfraction is filter after the gac whip attachment 0.5h of 0.1% (to regulate the quality of the waste water after pH for benchmark), the filtrate obtained is micro-yellow, adding massfraction is again filter after gac (to regulate the quality of the waste water after pH for benchmark) the whip attachment 0.5h of 0.1% to obtain almost colourless transparent filtrate, COD=150mg/L, saltiness 4%.
Embodiment 2
H acid waste water, in black, COD=26030mg/L, pH=2.
(1) H acid waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium;
(2) Bipolar Membrane process: utilize Bipolar Membrane process filtrate, obtains basic solution and massfraction is the sulfuric acid of 9%, and in basic solution, the massfraction of sodium hydroxide is 3.9%, and the massfraction of ammonia is 3.5%.The condition of Bipolar Membrane for individual membrane voltage be 1.5V, current density is 400A/m
2, temperature is 30 DEG C, and the treatment time is 100min.
(3) wet oxidation: by the pH regulator to 8 containing organic solution obtained after Bipolar Membrane process, then squeeze in wet oxidation still, be warming up to 250 DEG C, pressure 6MPa, lower the temperature after passing into atmospheric oxidation 1.5h.
Record out still waste water and show orange-yellow, pH=4.5, COD=2483mg/L, NH
3-N=165.0mg/L.
(4) adsorb: go out in still waste water to add in step (3) gac (to go out the quality of still waste water for benchmark) the whip attachment 30min that massfraction is 0.2%, suction filtration obtains yellowish treatment solution, its COD=1545mg/L.
Embodiment 3
H acid waste water, in black, COD=130000mg/L, pH=1.
(1) H acid waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium;
(2) Bipolar Membrane process: utilize Bipolar Membrane process filtrate, obtains basic solution and massfraction is the sulfuric acid of 11%, and in basic solution, the massfraction of sodium hydroxide is 4.5%, and the massfraction of ammonia is 4.5%.The condition of Bipolar Membrane for individual membrane voltage be 1.5V, current density is 600A/m
2, temperature is 30 DEG C, and the treatment time is 120min.
(3) wet oxidation: by the pH regulator 7 containing organic solution obtained after Bipolar Membrane process, then add in autoclave, pass into the air of 30atm, in 250 DEG C of reactions cooling after a hour;
Pressure release after cooling, then the air continuing to pass into 30atm continues in 250 DEG C of reactions cooling after a hour;
After cooling pressure release, then pass into the air of 30atm, react 1.5 hours at 250 DEG C.Water outlet is yellow, COD=6500mg/L, COD clearance 95%.
(4) decolour: in the water outlet of step (3), add massfraction is filter after gac (with the effluent characteristics of step (3) for benchmark) the whip attachment 30min of 0.3%, adding massfraction is again suction filtration after the charcoal absorption of 0.1%, filtrate is light yellow, surveys COD=6545mg/L.
Comparative example 1
Be that step (4) adopts ClO with the difference of embodiment 3
2decolouring, concrete operations are as follows:
The ClO of 0.2% is added in the water outlet of step (3)
2(ClO
2consumption with the quality of waste water for benchmark), 30min is reacted under normal temperature, add again massfraction be 0.1% gac (with the effluent characteristics of step (3) for benchmark) adsorb suction filtration after 30min, color is safran, and decolorizing effect is undesirable.
Comparative example 2
Be that step (4) adopts Fe/C to decolour with the difference of embodiment 3, concrete operations are as follows:
The water outlet pH=4 of pacing rapid (3), to add massfraction be 0.2% gac and massfraction is filter after 2% iron powder (with the effluent characteristics of step (3) for benchmark) reacts 4h, be adjusted to pH=8 again, suction filtration after flocculation 30min, filtrate is safran, and decolorizing effect is undesirable.
Embodiment 4
(1) refined naphthalene successively through sulfonation, nitrated, neutralization, reduction, T acid segregation, alkali fusion, H acid emanate prepare H acid.
(2) H acid segregation waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium;
(3) Bipolar Membrane process: the filtrate utilizing Bipolar Membrane treatment step (2), obtains basic solution and massfraction is the sulfuric acid of 9.8%, and in basic solution, the massfraction of sodium hydroxide is 3.7%, and the massfraction of ammonia is 3.7%.The condition of Bipolar Membrane for individual membrane voltage be 1.5V, current density is 450A/m
2, temperature is 30 DEG C, and the treatment time is 120min.
By this step gained sulfuric acid reuse to H acid segregation workshop section, steaming is revolved to gained basic solution, obtains sodium hydroxide reuse to alkaline melt workshop section.
(4) wet oxidation: by the pH regulator to 7 containing organic solution obtained after step (3) Bipolar Membrane process, then squeeze in wet oxidation still, be warming up to 250 DEG C, pressure 6MPa, lower the temperature after passing into atmospheric oxidation 1.5h.
Record out still waste water and show orange-yellow, pH=4.5, COD=2107mg/L.
(5) adsorb: step (4) go out in still waste water to add massfraction be 0.3% gac (to go out the quality of still waste water for benchmark) adsorb 30min, suction filtration obtains flaxen treatment solution, then pH to 6.0 is regulated, color becomes yellow, add again massfraction be 0.2% gac (to go out the quality of still waste water for benchmark) adsorb 30min, suction filtration obtains yellowish treatment solution, its COD=1487mg/L.
(6) T acid segregation waste water is filtered, to remove the material such as suspended substance and iron, calcium, magnesium;
(7) Bipolar Membrane process: the filtrate utilizing Bipolar Membrane treatment step (6), obtains basic solution and massfraction is the sulfuric acid of 9.8%, by this sulfuric acid reuse to T acid segregation workshop section.The condition of Bipolar Membrane for individual membrane voltage be 1.5V, current density is 450A/m
2, temperature is 30 DEG C, and the treatment time is 120min.
(8) wet oxidation: by the pH regulator to 8 containing organic solution obtained after step (7) Bipolar Membrane process, add the CuSO that massfraction is 0.5%
45H
2o is as catalyzer (with T acid segregation wastewater quality for benchmark), 3h is reacted under temperature 260 DEG C, pressure 7MPa condition, reaction terminates the filtrate (i.e. filtrate I) that rear suction filtration obtains oyster, and its about pH=2.1, COD clearance are 85%.
(9) in filtrate I, the FeSO that massfraction is 0.5% is added
47H
2o (with T acid segregation wastewater quality for benchmark), treats FeSO
47H
2after O dissolves completely, add the liquid caustic soda adjustment pH=8.5 that massfraction is 5.5%, flocculation 30min, suction filtration obtains blue filtrate II.
(10) in filtrate II, the Na that massfraction is 0.6% is added
2s9H
2o (with T acid segregation wastewater quality for benchmark), reaction 30min, removing complex copper, suction filtration obtains filtrate III for black (CuS particle is less, and part enters in filtrate).
(11) in filtrate III, add vitriol oil readjustment pH=6.0, adding massfraction is that 0.2% gac (with T acid segregation wastewater quality for benchmark) adsorbs 30min, and obtain subdiaphanous filtrate, its COD clearance is 96%.
Claims (8)
1. a waste water desalination purifying method for resource utilization, is characterized in that, comprise the following steps:
(1) utilize Bipolar Membrane to process salt-containing organic wastewater, obtain containing the organic aqueous solution, and acidic solution and basic solution;
(2) in pH=2 ~ 12, pressure is 2 ~ 8MPa, and temperature is under the condition of 180 ~ 300 DEG C, carries out wet oxidation, obtain treatment solution to containing organic solution;
(3) aftertreatment is carried out to treatment solution and obtain water outlet.
2. the waste water desalination purifying method of resource utilization as claimed in claim 1, is characterized in that, filter in advance before utilizing Bipolar Membrane to process salt-containing organic wastewater.
3. the waste water desalination purifying method of resource utilization as claimed in claim 1, is characterized in that, in step (1), the treatment condition of Bipolar Membrane are: the voltage <2.5V of individual film, current density is 100 ~ 600A/m
2, temperature is 1 ~ 40 DEG C.
4. the waste water desalination purifying method of resource utilization as claimed in claim 1, is characterized in that, described aftertreatment is flocculation and/or decolouring.
5. the waste water desalination purifying method of resource utilization as claimed in claim 1, is characterized in that, adopt sorbent material decolouring in step (3), the add-on of sorbent material is 0.05 ~ 0.5% for the treatment of solution quality.
6. the waste water desalination purifying method of resource utilization as claimed in claim 1, is characterized in that, in step (2), the time of wet oxidation is 2 ~ 6h.
7. the production technique of the H acid improved, refined naphthalene successively through sulfonation, nitrated, neutralization, reduction, T acid segregation, alkali fusion, H acid emanate prepare H acid, it is characterized in that, H acid segregation produce waste water successively after filtration with Bipolar Membrane process, obtain sulfuric acid and sodium hydroxide, this sulfuric acid and sodium hydroxide are back in industrial production.
8. the production technique of the as claimed in claim 7 H acid improved, is characterized in that, the waste water that T acid segregation produces successively after filtration with Bipolar Membrane process, obtain sulfuric acid and ammoniacal liquor, sulfuric acid and ammoniacal liquor are back in industrial production.
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Cited By (4)
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| CN105236631A (en) * | 2015-11-27 | 2016-01-13 | 福建创源环保有限公司 | Method for treating high-salt industrial wastewater based on multi-electrode multi-diaphragm electrolytic cell |
| CN105566176A (en) * | 2015-11-26 | 2016-05-11 | 浙江奇彩环境科技股份有限公司 | Improved 6-nitro-1-diazo-2-naphthol-4-sulphonic acid production process |
| CN106587494A (en) * | 2016-12-06 | 2017-04-26 | 浙江力禾集团有限公司 | Method for improving ammonia-nitrogen content of H acid wastewater |
| CN106830492A (en) * | 2017-04-05 | 2017-06-13 | 利民化工股份有限公司 | A kind of processing method of methoxy acrylic Pesticidal products waste water |
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| CN102910853A (en) * | 2011-08-03 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for producing naphthalene-based superplasticizer by using H acid wastewater recovered solution |
| CN104150722A (en) * | 2014-09-04 | 2014-11-19 | 北京赛科康仑环保科技有限公司 | Treatment process for acrylic fiber waste water |
| CN104261591A (en) * | 2014-10-08 | 2015-01-07 | 上海博丹环境工程技术有限公司 | Method and system for treating high-concentration salt-containing wastewater from prochloraz aminating working section |
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| CN102910853A (en) * | 2011-08-03 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for producing naphthalene-based superplasticizer by using H acid wastewater recovered solution |
| CN104150722A (en) * | 2014-09-04 | 2014-11-19 | 北京赛科康仑环保科技有限公司 | Treatment process for acrylic fiber waste water |
| CN104261591A (en) * | 2014-10-08 | 2015-01-07 | 上海博丹环境工程技术有限公司 | Method and system for treating high-concentration salt-containing wastewater from prochloraz aminating working section |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566176A (en) * | 2015-11-26 | 2016-05-11 | 浙江奇彩环境科技股份有限公司 | Improved 6-nitro-1-diazo-2-naphthol-4-sulphonic acid production process |
| CN105236631A (en) * | 2015-11-27 | 2016-01-13 | 福建创源环保有限公司 | Method for treating high-salt industrial wastewater based on multi-electrode multi-diaphragm electrolytic cell |
| CN106587494A (en) * | 2016-12-06 | 2017-04-26 | 浙江力禾集团有限公司 | Method for improving ammonia-nitrogen content of H acid wastewater |
| CN106830492A (en) * | 2017-04-05 | 2017-06-13 | 利民化工股份有限公司 | A kind of processing method of methoxy acrylic Pesticidal products waste water |
| CN106830492B (en) * | 2017-04-05 | 2021-04-20 | 利民化学有限责任公司 | Treatment method of methoxy acrylic ester pesticide product wastewater |
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