CN106007110A - Low-salt wastewater recycled treatment and recycling method - Google Patents
Low-salt wastewater recycled treatment and recycling method Download PDFInfo
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- CN106007110A CN106007110A CN201610436947.6A CN201610436947A CN106007110A CN 106007110 A CN106007110 A CN 106007110A CN 201610436947 A CN201610436947 A CN 201610436947A CN 106007110 A CN106007110 A CN 106007110A
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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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- 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
- C02F1/44—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
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a low-salt wastewater recycled treatment and recycling method. Wastewater is obtained after pretreatment is conducted to remove organic matter, and the main ingredient is inorganic salt. The method includes the steps that low-salt wastewater is subjected to membrane distillation processing, and a concentrated solution and condensate water (1) are obtained; the concentrated solution is subjected to bipolar membrane electrodialysis processing, and corresponding dilute acid and dilute alkali with high value are obtained respectively; the dilute acid is subjected to membrane distillation concentration, a high-concentration acid solution and condensate water (2) are obtained, the dilute alkali is subjected to membrane distillation concentration, and a high-concentration alkali solution and condensate water (3) are obtained. The condensate water obtained through membrane distillation can be used for bipolar membrane electrodialysis processing and recycled as absorption liquid of acid and alkali, and discharge of wastewater is reduced.
Description
One, technical field
The present invention relates to a kind of less salt waste water reclaiming and process recovery method.
Two, background technology
In chemical process, inevitably produce many salt-containing organic wastewaters, wherein contain and have in a large number
Machine thing and salt constituents, in order to protect environment, need to process to reach discharge standard to these waste water.
Membrane Materials is a kind of employing dewatering microporous film, the membrance separation with film both sides steam pressure difference as mass transfer driving force
Process.During Membrane Materials, steam can enter fenestra, and liquid then can not pass through fenestra.Membrane Materials excellent
Gesture is mainly: it is good to produce water water quality, and salt rejection rate is high, and Water Sproading rate is high, can carry out at ambient pressure, equipment is simple,
Easy to operate.
The dense water of Membrane Materials that Membrane Materials obtains typically uses evaporative crystallization process to obtain salt-pepper noise, and this method reclaims
Salt is relatively costly, inferior quality, and recovery value is the highest.
Bipolar membrane electrodialysis can make the salt ion in saline solution and the hydrion of Bipolar Membrane both sides water decomposition and hydrogen
Oxygen radical ion combines and generates corresponding bronsted lowry acids and bases bronsted lowry, and the recycling of soda acid is worth just much higher than salt, and
And can be with direct reuse in Chemical Manufacture.
Three, summary of the invention
The present invention provides the recycling treatment recovery method of a kind of less salt waste water, it is possible to become by the salt in waste water
Divide and recycle, and resource utilization rate is high.
Concrete, the technical solution used in the present invention is:
A kind of less salt waste water reclaiming processes recovery method, and described less salt waste water is to remove organic through pretreatment
The waste water of thing, is mainly composed of inorganic salt, and described inorganic salt is XaYb, X is Na+、NH4 +、K+Deng,
Y is Cl-、SO4 2-Deng, a is the quantivalence absolute value of Y, and b is the quantivalence absolute value of X；Further,
Inorganic salt is usually sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, ammonium chloride etc., inorganic salt in waste water
Mass percentage concentration is generally 0.2～10%.Said method comprising the steps of:
(1) Membrane Materials processes: is processed through Membrane Materials by less salt waste water, obtains concentrated solution and condensed water 1；
(2) bipolar membrane electrodialysis processes: the concentrated solution obtained in step (1) processes through bipolar membrane electrodialysis,
Respectively obtain corresponding diluted acid HaY and diluted alkaline X (OH)bAnd the weak brine after processing；
(3) membrane distillation concentration bronsted lowry acids and bases bronsted lowry: the diluted acid H obtained in step (2)aY through membrane distillation concentration,
Obtain the H of high concentrationaY acid solution and condensed water 2, the diluted alkaline X (OH) that step (2) obtainsbSteam through film
Evaporate concentration, obtain the X (OH) of high concentrationbAqueous slkali and condensed water 3；
Further, in the inventive method, the condensed water 1 of step (1) and condensed water 2 He of step (3)
Condensed water 3 can be back to step (2) bipolar membrane electrodialysis process in, can as the acid in Bipolar Membrane,
Alkali absorption liquid.
High concentration H obtained in step (3)aY acid solution and X (OH)bIt is raw that aqueous slkali can be back to industry
In product.
Described brine waste be through pretreatment remove organic waste water, described preprocess method include but not
Be limited to light electrolysis, Fenton process, adsorb, flocculate, wet oxidation, low temperature wet oxidation, photocatalysis, extraction
Etc. one or more combination of method, the removing that these methods are well known to those skilled in the art has
The method of machine thing.
As preferably, in step (1), the concentration that treatment fluid processes, through Membrane Materials, the concentrated solution obtained is 10%
To 40%, more preferably 10% to 20%, the temperature range of Membrane Materials is 20 DEG C to 100 DEG C, more preferably
50 DEG C to 70 DEG C.
As preferably, the salt concentration of the weak brine after the process that step (2) obtains is 0.5% to 10%, when
When weak brine concentration after Bipolar Membrane process is less than 5%, energy consumption and cost that Bipolar Membrane processes significantly rise, institute
With it is further preferred that the weak brine concentration after Chu Liing is for 5% to 10%；And the weak brine after processing mixes with raw wastewater
Conjunction is recycled by method of the present invention after carrying out pretreatment again, or is returned directly in step (1),
As preferably, the weak brine after process returns to step (1), mixes with less salt waste water, and circulation carries out step (1)
Membrane Materials process.The diluted acid H obtainedaThe concentration of Y is 2-10%, preferably 6%-10%, the diluted alkaline obtained
X(OH)bConcentration be 2-8%, preferably 3-8%.
As preferably, the H of the high concentration that the membrane distillation concentration of step (3) obtainsaThe concentration of Y acid solution is
10-50%, preferably 20-50%；The X (OH) of the high concentration obtainedbThe concentration of aqueous slkali is 8-40%, preferably
20-30%；The temperature range of Membrane Materials is 20-100 DEG C, preferably 50-80 DEG C, more preferably 50～60 DEG C.
The reaction condition that bipolar membrane electrodialysis of the present invention processes is: use titanium to be coated with ruthenium in Bipolar Membrane system
As electrode, diaphragm is homogeneous membrane or heterogeneous membrane, uses 0.1-5% strong electrolyte (such as sodium sulfate) solution
For pole liquid, temperature 0～40 DEG C, electric current density is 100-600A/cm2.Employing well known to a person skilled in the art
Bipolar membrane electrodialysis device carries out processing.The technique that bipolar membrane electrodialysis processes also is skill known in this field
Art.
The beneficial effects of the present invention is, the concentration of brine waste is concentrated by Membrane Materials for the first time, is conducive to carrying
The efficiency that high follow-up Bipolar Membrane processes.By bipolar membrane electrodialysis, the salt constituents in waste water is dissociated into utilization
Costly acid is with alkali, and the saline after process returns to Membrane Materials circular treatment for the first time.Twice Membrane Materials obtains
Condensed water may be used for bipolar membrane electrodialysis process in, as acid, the absorbing liquid reuse of alkali, decrease useless
Water discharges, and the concentration of acid, alkali is improved by Membrane Materials for the second time, can be with direct reuse in commercial production.And
And use membrane distillation concentration equipment simple, cost-effective.
Four, detailed description of the invention
With specific embodiment, technical scheme is described further below, but the protection of the present invention
Scope is not limited to this.
Embodiment 1
Diallyl mother liquor waste water, is mainly composed of amino benzene derivate, at ferrum-charcoal reaction and activated carbon
After reason, COD about 2300mg/L, ammonium chloride content about 6.5%.
(1) Membrane Materials processes: aqueous ammonium chloride solution, through distillation membrance concentration, reaction temperature 55 DEG C, obtains 40%
Ammonium chloride concentrated solution and condensed water 1；
(2) Bipolar Membrane processes: the high concentration 40% ammonium chloride concentrated solution obtained in step (1) is through bipolar
EDBM processes, and obtains 7% dilute hydrochloric acid and 3.5% weak ammonia；Waste water salinity after process is about 6%,
It is mixed into distillation membrance concentration circular treatment with the ammonium chloride solution in step (1)；Bipolar Membrane system uses
It is homogeneous membrane as electrode, diaphragm that titanium is coated with ruthenium, and using 1% metabisulfite solution is pole liquid, temperature 40 DEG C, electric current
Density is 200A/cm2。
(3) Membrane Materials: the dilute hydrochloric acid that obtains in step (2) and weak ammonia respectively through distillation membrance concentration,
Reaction temperature 60 DEG C, obtains 30% concentrated hydrochloric acid and 10% strong aqua ammonia, and condensed water 2 and condensed water 3；
(4) concentrated hydrochloric acid obtained in step (3) and strong aqua ammonia can be back to industry, step (1) and (3)
In the hydrogen chloride that may be used in step (2) in bipolar membrane electrodialysis of the condensed water 1,2,3 that obtains and ammonia
Absorbing liquid.
Embodiment 2
In DASA and filtrate, after ozone oxidation and activated carbon adsorption, COD about 1200mg/L, sulphuric acid
Sodium content about 4.7%.
(1) Membrane Materials processes: aqueous sodium persulfate solution, through distillation membrance concentration, reaction temperature 65 DEG C, obtains 20%
Sodium sulfate concentrated solution and condensed water 1；
(2) Bipolar Membrane processes: the 20% sodium sulfate concentrated solution obtained in step (1) is through Bipolar Membrane electric osmose
Analysis processes, and obtains 8% dilute sulfuric acid and 8% dilute sodium hydroxide, and the waste water salinity after process is about 5%, with step
Suddenly the aqueous sodium persulfate solution in (1) is mixed into distillation membrance concentration circular treatment；Bipolar Membrane system uses titanium
Being coated with ruthenium is homogeneous membrane as electrode, diaphragm, and using 2% metabisulfite solution is pole liquid, and temperature 35 DEG C, electric current is close
Degree is 100A/cm2。
(3) Membrane Materials: the dilute sulfuric acid and the dilute sodium hydroxide that obtain in step (2) are dense respectively through distillation film
Contracting, reaction temperature 60 DEG C, obtain 40% concentrated sulphuric acid and 40% concentrated sodium hydroxide, and condensed water 2 and condensed water
3；
(4) concentrated sulphuric acid obtained in step (3) and concentrated sodium hydroxide can be back to industry, step (1)
(3) condensed water 1,2,3 obtained in may be used for the sulphuric acid in step (2) and the suction of sodium hydroxide
Receive liquid.
Embodiment 3
Acid Dye Wastewater, after ozone oxidation and activated carbon adsorption, solution C OD about 1800mg/L, chlorine
Change sodium content and be about 3.5%.
(1) Membrane Materials processes: sodium-chloride water solution, through distillation membrance concentration, reaction temperature 50 DEG C, obtains highly concentrated
20% sodium chloride concentrated solution of degree and condensed water 1；
(2) Bipolar Membrane processes: the 20% sodium chloride concentrated solution obtained in step (1) is through Bipolar Membrane electric osmose
Analysis processes, and obtains 7% dilute hydrochloric acid and 8% dilute sodium hydroxide, and the waste water salinity after process is about 8%, with step
Suddenly the sodium-chloride water solution in (1) is mixed into distillation membrance concentration circular treatment；Bipolar Membrane system uses titanium
Being coated with ruthenium is homogeneous membrane as electrode, diaphragm, and using 1% metabisulfite solution is pole liquid, and temperature 30 DEG C, electric current is close
Degree is 400A/cm2。
(3) Membrane Materials: the dilute hydrochloric acid and the dilute sodium hydroxide that obtain in step (2) are dense respectively through distillation film
Contracting, reaction temperature 60 DEG C, obtain 30% concentrated hydrochloric acid and 40% concentrated sodium hydroxide, and condensed water 2 and condensed water
3；
(4) concentrated hydrochloric acid obtained in step (3) and concentrated sodium hydroxide can be back to industry, step (1)
(3) obtain in condensed water 1,2,3 may be used for the hydrogen chloride in step (2) and sodium hydroxide
Absorbing liquid.
Claims (10)
1. less salt waste water reclaiming processes a recovery method, and described less salt waste water is main component after pretreatment
For the waste water of inorganic salt, described inorganic salt is XaYb, X is Na+、NH4 +Or K+, Y is Cl-Or SO4 2-,
A is the quantivalence absolute value of Y, and b is the quantivalence absolute value of X；Said method comprising the steps of:
(1) Membrane Materials processes: is processed through Membrane Materials by less salt waste water, obtains concentrated solution and condensed water 1；
(2) bipolar membrane electrodialysis processes: the concentrated solution obtained in step (1) processes through bipolar membrane electrodialysis,
Respectively obtain corresponding diluted acid HaY and diluted alkaline X (OH)b, and the weak brine after process；
(3) membrane distillation concentration bronsted lowry acids and bases bronsted lowry: the diluted acid H obtained in step (2)aY through membrane distillation concentration,
Obtain the H of high concentrationaY acid solution and condensed water 2, the diluted alkaline X (OH) that step (2) obtainsbSteam through film
Evaporate concentration, obtain the X (OH) of high concentrationbAqueous slkali and condensed water 3.
2. the method for claim 1, it is characterised in that the quality hundred of inorganic salt in described less salt waste water
Dividing content range is 0.2%～10%.
3. the method for claim 1, it is characterised in that the condensed water 1 of described step (1) and step
Suddenly condensed water 2 and the condensed water 3 of (3) is back in the bipolar membrane electrodialysis process of step (2), as
Acid in Bipolar Membrane, Alkali absorption liquid.
4. the method for claim 1, it is characterised in that the high concentration obtained in described step (3)
HaY acid solution and high concentration X (OH)bAqueous slkali is back in commercial production.
5. the method for claim 1, it is characterised in that in described step (1), through Membrane Materials
The concentration processing the concentrated solution obtained is 10-40%, and the temperature of Membrane Materials is 20-100 DEG C.
6. the method for claim 1, it is characterised in that the membrane distillation concentration of described step (3) obtains
The H of the high concentration arrivedaThe concentration of Y acid solution is 10-50%；The X (OH) of the high concentration obtainedbAqueous slkali
Concentration is 8%-40%；The temperature range of Membrane Materials is 20-100 DEG C.
7. the method for claim 1, it is characterised in that the Bipolar Membrane system of described step (2) obtains
The diluted acid H arrivedaThe concentration of Y is 2-10%；The diluted alkaline X (OH) obtainedbConcentration be 2%-8%, obtain
The concentration range of the weak brine after process is 0.5-10%.
8. the method for claim 1, it is characterised in that in described step (1), through Membrane Materials
The concentration processing the concentrated solution obtained is 10-20%, and the temperature range of Membrane Materials is 50-70 DEG C.
9. the method for claim 1, it is characterised in that in described step (3), membrane distillation concentration
The H of the high concentration obtainedaThe concentration of Y acid solution is 20-50%；The X (OH) of the high concentration obtainedbAqueous slkali
Concentration be 20-30%；The temperature range of Membrane Materials is 50-80 DEG C.
10. method as claimed in claim 7, it is characterised in that the Bipolar Membrane system of described step (2) obtains
To process after the concentration range of weak brine be 5-10%, and the weak brine obtained is returned to step (1), with
Less salt waste water mixes, and circulation carries out Membrane Materials process.
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Cited By (7)
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| CN107188358A (en) * | 2017-07-19 | 2017-09-22 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment system, processing method and the application of high-concentration ammonium salt waste water |
| CN107215996A (en) * | 2017-07-19 | 2017-09-29 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment system, processing method and the application of high concentration sodium salt waste water |
| CN110282786A (en) * | 2019-06-14 | 2019-09-27 | 江苏卓博环保科技有限公司 | Recycle waste lithium cell positive electrode waste water reclaiming processing unit and method |
| CN111039487A (en) * | 2020-01-06 | 2020-04-21 | 大唐环境产业集团股份有限公司 | Desulfurization wastewater treatment system and treatment method |
| CN113069900A (en) * | 2021-04-26 | 2021-07-06 | 萍乡市华星环保工程技术有限公司 | Flue gas desulfurization and sulfur-containing waste liquid recycling coupling process |
| CN113213685A (en) * | 2021-04-26 | 2021-08-06 | 萍乡市华星环保工程技术有限公司 | Desulfurization product sulfur recycling treatment process |
| CN113292190A (en) * | 2021-05-27 | 2021-08-24 | 福州大学 | Membrane distillation and bipolar membrane electrodialysis combined wastewater treatment system |
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| CN107215996A (en) * | 2017-07-19 | 2017-09-29 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment system, processing method and the application of high concentration sodium salt waste water |
| CN110282786A (en) * | 2019-06-14 | 2019-09-27 | 江苏卓博环保科技有限公司 | Recycle waste lithium cell positive electrode waste water reclaiming processing unit and method |
| CN111039487A (en) * | 2020-01-06 | 2020-04-21 | 大唐环境产业集团股份有限公司 | Desulfurization wastewater treatment system and treatment method |
| CN113069900A (en) * | 2021-04-26 | 2021-07-06 | 萍乡市华星环保工程技术有限公司 | Flue gas desulfurization and sulfur-containing waste liquid recycling coupling process |
| CN113213685A (en) * | 2021-04-26 | 2021-08-06 | 萍乡市华星环保工程技术有限公司 | Desulfurization product sulfur recycling treatment process |
| CN113292190A (en) * | 2021-05-27 | 2021-08-24 | 福州大学 | Membrane distillation and bipolar membrane electrodialysis combined wastewater treatment system |
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