CN111252982A - Method and device for treating high-salt high-COD wastewater - Google Patents
Method and device for treating high-salt high-COD wastewater Download PDFInfo
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- 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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- C02F1/22—Treatment of water, waste water, or sewage by freezing
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- 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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- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- 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
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- C02F2101/30—Organic 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
The invention provides a method and a device for treating high-salt high-COD wastewater. The high-salt high-COD wastewater contains Na with the mass concentration of 30-40%2SO4And the COD value is 10000-30000 mg/L, and the treatment method comprises the following steps: s1, performing low-temperature freezing treatment on the high-salt high-COD wastewater at the treatment temperature of-5-10 ℃ to obtain a solid phase and pretreated wastewater; s2, electrolyzing the pretreated wastewater to obtain electrolyzed wastewater; s3, adjusting the pH value of the electrolytic wastewater to 2.0-4.0 to separate out organic matters in the electrolytic wastewater to obtain acid-adjusting wastewater; and S4, carrying out physical adsorption and decoloration on the acid-exchanged wastewater to obtain treated wastewater. The method for treating the high-salt high-COD wastewater has the advantages of good treatment effect, relative energy consumption, convenient operation and short treatment time, and is very suitable for wide application.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method and a device for treating high-salinity high-COD wastewater.
Background
With the rapid development of industrial production, the discharge amount of industrial wastewater is increasing day by day, and wastewater treatment is always a key research point at home and abroad. And the treatment of the high-salt organic wastewater is an industrial difficulty, and the development of an economic and efficient high-salt organic wastewater treatment technology is always a hotspot in the field of water pollution control engineering. The prior methods for treating COD wastewater comprise a plurality of methods, such as a chemical method, a biological method and an evaporative crystallization method. But neither chemical method nor biological method can effectively solve the problem of standard discharge of high-salinity wastewater treatment, and the single evaporative crystallization method has the problems of high energy consumption and difficult market sale of the produced products.
In patent CN109422385, a method for treating high-salt wastewater in metallurgical industry is proposed, in which high-salt wastewater is electrolyzed, filtered and added with a compound agent consisting of polymeric ferric sulfate, polymeric aluminum sulfate and potassium permanganate. In patent CN105152249B, a process for evaporative crystallization of metallurgical high-concentration salt-containing wastewater is proposed, which adopts a multi-effect evaporation technique and a mechanical thermal compression technique, wherein the high-concentration salt-containing wastewater does not refer to the COD content in the wastewater, and the applicability of the high-concentration salt-containing wastewater cannot be judged. In patent CN105236651A, a process for evaporative crystallization of high-concentration salt-containing wastewater from pulp making and paper making is proposed, which also does not mention the COD content in the wastewater.
Therefore, there is a need to provide a high-salt high-COD wastewater treatment process with relatively low energy consumption and more efficient treatment.
Disclosure of Invention
The invention mainly aims to provide a method and a device for treating high-salt high-COD wastewater, so as to solve the problems of high energy consumption or low efficiency in the treatment of the high-salt high-COD wastewater in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for treating high-salt high-COD wastewater containing 30 to 40% by mass of Na2SO4And the COD value is 10000-30000 mg/L, and the treatment method comprises the following steps: s1, low-temperature freezing treatment is carried out on the high-salt high-COD wastewaterAnd the treatment temperature is-5-10 ℃, so as to obtain a solid phase and pretreated wastewater; s2, electrolyzing the pretreated wastewater to obtain electrolyzed wastewater; s3, adjusting the pH value of the electrolytic wastewater to 2.0-4.0 to separate out organic matters in the electrolytic wastewater to obtain acid-adjusting wastewater; and S4, carrying out physical adsorption and decoloration on the acid-exchanged wastewater to obtain treated wastewater.
Further, in step S1, the temperature of the low-temperature freezing treatment is 0 to 10 ℃.
Further, in the step S2, in the process of electrolyzing the pretreated wastewater, the electrolysis current is 1-5A, and the electrolysis time is 60-120 min.
Further, the pH value of the high-salt high-COD wastewater is 5.0-10.0; preferably, in step S4, activated carbon is used to physically adsorb and decolorize the acid-exchanged wastewater.
Further, in step S3, the pH value of the electrolytic wastewater is adjusted using sulfuric acid.
Further, in step S2, in the process of electrolyzing the pretreated wastewater, the adopted electrolysis electrode is a titanium alloy material, preferably, the material of the electrolysis electrode comprises titanium and alloy elements, and the alloy elements are one or more of platinum, ruthenium, iridium, lead and tin.
According to another aspect of the invention, the invention also provides a treatment device for the high-salt high-COD wastewater, wherein the high-salt high-COD wastewater contains Na with the mass concentration of 30-40%2SO4And the COD value is 10000 ~ 30000mg/L, the processing device includes: the low-temperature freezing unit is used for performing low-temperature freezing treatment on the high-salt high-COD wastewater at the temperature of-5-10 ℃ to obtain pretreated wastewater; the electrolysis unit is connected with the low-temperature freezing unit and is used for carrying out electrolysis treatment on the pretreated wastewater to obtain electrolysis wastewater; the acid regulating unit is connected with the electrolysis unit and is used for regulating the pH value of the electrolysis wastewater to 2.0-4.0 to obtain acid regulating wastewater; and the physical adsorption and decoloration unit is connected with the acid regulating unit and is used for carrying out physical adsorption and decoloration treatment on the acid regulating wastewater.
Further, the electrolysis unit comprises an electrolysis bath and electrolysis electrodes positioned in the electrolysis bath, wherein the electrolysis electrodes are made of titanium alloy materials, preferably, the materials of the electrolysis electrodes comprise titanium and alloy elements, and the alloy elements are one or more of platinum, ruthenium, iridium, lead and tin.
Further, activated carbon is adopted in a physical adsorption and decolorization unit for physical adsorption and decolorization treatment.
Further, the low-temperature freezing unit comprises a low-temperature freezing device and a filtering device which are connected in series, wherein the low-temperature freezing device is used for performing low-temperature freezing treatment, and the filtering device is used for filtering a product of the low-temperature freezing treatment to obtain the pretreated wastewater.
The invention provides a method for treating high-salt high-COD wastewater, which uses Na with the mass concentration of 30-40%2SO4And the COD value is 10000-30000 mg/L. In the treatment process, firstly, the wastewater is frozen at a low temperature of-5-10 ℃, and the step can lead Na in the wastewater to be2SO4Converted into mirabilite Na2SO4·10H2O is crystallized and this crystallization is more sufficient at this temperature. After low-temperature freezing treatment, the invention further electrolyzes the pretreated wastewater, so that the non-adsorbable long-chain organic matters can be decomposed into short-chain organic matters. Then, the acid adjusting treatment can separate out the short-chain organic matters and other organic matters, and remove the short-chain organic matters and other organic matters through the final physical adsorption and decolorization treatment steps.
The method for treating the high-salt high-COD wastewater has the advantages of good treatment effect, relative energy consumption, convenient operation and short treatment time, and is very suitable for wide application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a flow diagram of a method for treating high salinity high COD wastewater according to one embodiment of the present invention; and
FIG. 2 is a block diagram showing the structure of a high-salinity high-COD wastewater treatment apparatus according to an embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. a low temperature freezing unit; 20. an electrolysis unit; 30. an acid regulating unit; 40. a physical adsorption and decolorization unit.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background section, the prior art has problems of high energy consumption or insufficient efficiency in treating high-salt high-COD wastewater.
In order to solve the problem, the invention provides a method for treating high-salt high-COD wastewater, wherein the high-salt high-COD wastewater contains 30-40% of Na by mass concentration2SO4And the COD value is 10000-30000 mg/L, as shown in figure 1, the treatment method comprises the following steps: s1, performing low-temperature freezing treatment on the high-salt high-COD wastewater at the treatment temperature of-5-10 ℃ to obtain a solid phase and pretreated wastewater; s2, electrolyzing the pretreated wastewater to obtain electrolyzed wastewater; s3, adjusting the pH value of the electrolytic wastewater to 2.0-4.0 to separate out organic matters in the electrolytic wastewater to obtain acid-adjusting wastewater; and S4, carrying out physical adsorption and decoloration on the acid-exchanged wastewater to obtain treated wastewater.
In the treatment process, firstly, the wastewater is frozen at a low temperature of-5-10 ℃, and the step can lead Na in the wastewater to be2SO4Converted into mirabilite Na2SO4·10H2O is crystallized and this crystallization is more sufficient at this temperature. After low-temperature freezing treatment, the invention further electrolyzes the pretreated wastewater, so that the non-adsorbable long-chain organic matters can be decomposed into short-chain organic matters. Then, the acid adjusting treatment can separate out the short-chain organic matters and other organic matters, and remove the short-chain organic matters and other organic matters through the final physical adsorption and decolorization treatment steps. The method for treating the high-salt high-COD wastewater has the advantages of good treatment effect, relative energy consumption, convenient operation and short treatment time, and is very suitable for wide application.
Besides the advantages, the method adopts an electrolysis treatment mode to decompose long-chain organic matters in the pretreated wastewater, does not generate waste residues, and also has a certain decolorizing function.
To make Na in the wastewater2SO4More sufficient conversion to the precipitation of mirabilite crystals is achieved, and in a preferred embodiment, in the step S1, the temperature of the low-temperature freezing treatment is 0 to 10 ℃. After the low-temperature freezing treatment, solid-liquid separation is preferably carried out by adopting a filtering mode to obtain a solid phase and the pretreated wastewater, wherein the solid phase is a solid salt component and can be used for recycling salt, and the pretreated wastewater is subjected to subsequent treatment.
In a preferred embodiment, in the step S2, during the electrolysis of the pretreated wastewater, the electrolysis current is 1-5A, and the electrolysis time is 60-120 min. Under the condition of the electrolysis process, the long-chain organic matters which cannot be adsorbed in the wastewater can be decomposed into short-chain organic matters more fully.
In order to make the wastewater treatment more efficient, in a preferred embodiment, the pH value of the high-salt high-COD wastewater is 5.0-10.0; preferably, in step S4, activated carbon is used to physically adsorb and decolorize the acid-exchanged wastewater. The activated carbon has the advantages of good adsorption effect, low cost and the like, and the activated carbon after physical adsorption and decoloration can be recycled.
In a preferred embodiment, in step S3, the pH of the electrolytic wastewater is adjusted by using sulfuric acid. The pH value is adjusted by adopting sulfuric acid, no new impurities are additionally introduced, and the adjustment is more effective.
In a more preferred embodiment, the electrolysis electrode used in the step S2 of electrolyzing the pretreated wastewater is a titanium alloy material, preferably the material of the electrolysis electrode comprises titanium and an alloy element, and the alloy element is one or more of platinum, ruthenium, iridium, lead and tin. The titanium alloy is corrosion resistant, and the precious metal coated on the surface is not easy to dissolve in the electrolytic process and plays a role in catalytic oxidation.
According to another aspect of the invention, there is also provided a device for treating high-salt high-COD wastewater containing 30E to E40% of Na2SO4And the COD value is 10000-30000 mg/L, as shown in figure 2, the treatment device comprises a low-temperature freezing unit 10, an electrolysis unit 20, an acid regulating unit 30 and a physical adsorption and decolorization unit 40, wherein the low-temperature freezing unit 10 is used for performing low-temperature freezing treatment on high-salt high-COD wastewater at the temperature of-5-10 ℃ to obtain pretreated wastewater; the electrolysis unit 20 is connected with the low-temperature freezing unit 10 and is used for carrying out electrolysis treatment on the pretreated wastewater to obtain electrolysis wastewater; the acid regulating unit 30 is connected with the electrolysis unit 20 and is used for regulating the pH value of the electrolysis wastewater to 2.0-4.0 to obtain acid regulating wastewater; the physical adsorption and decoloration unit 40 is connected with the acid regulating unit 30 and is used for carrying out physical adsorption and decoloration treatment on the acid regulating wastewater.
The device is used for treating high-salt high-COD wastewater, the wastewater is firstly frozen at a low temperature of-5-10 ℃, and Na in the wastewater can be treated by the step2SO4Converted into mirabilite Na2SO4·10H2O is crystallized and this crystallization is more sufficient at this temperature. After low-temperature freezing treatment, the invention further electrolyzes the pretreated wastewater, so that the non-adsorbable long-chain organic matters can be decomposed into short-chain organic matters. Then, the acid adjusting treatment can separate out the short-chain organic matters and other organic matters, and remove the short-chain organic matters and other organic matters through the final physical adsorption and decolorization treatment steps. The device is adopted to treat high-salt high-COD wastewater, has good treatment effect, relative energy consumption angle, convenient operation and short treatment time, and is very suitable for wide application.
In a preferred embodiment, the electrolysis unit 20 comprises an electrolysis cell and an electrolysis electrode positioned in the electrolysis cell, the electrolysis electrode is a titanium alloy material, preferably the material of the electrolysis electrode comprises titanium and an alloying element, and the alloying element is one or more of platinum, ruthenium, iridium, lead and tin. More preferably, the physical adsorption and decoloring unit 40 performs physical adsorption and decoloring treatment using activated carbon.
In a preferred embodiment, the cryogenic freezing unit 10 comprises a cryogenic freezing device and a filtering device arranged in series with each other, the cryogenic freezing device being configured to perform a cryogenic freezing process, and the filtering device being configured to filter a product of the cryogenic freezing process to obtain a pre-treated wastewater.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
High salt and high COD 1# waste water treatment, Na2SO4The concentration is close to saturation, the mass concentration is 30 percent, and the COD concentration is about 30000 mg/L. First, low-temperature freezing treatment is carried out at 5 ℃ to make Na2SO4Crystallizing to obtain Natrii sulfas; filtering to obtain solid salt and pretreated wastewater; then, feeding the pretreated wastewater into an electrolytic cell, and electrolyzing for 2 hours under the current of 2A to obtain electrolytic wastewater; adjusting the pH value of the electrolytic wastewater to 2.5 by adopting sulfuric acid, and standing for 10min to obtain acid-adjusted wastewater; and finally, carrying out physical adsorption and decoloration on the acid-exchange wastewater by using active carbon, adsorbing the separated organic matters, and carrying out final decoloration treatment. The COD removal rate is about 95 percent through detection.
Example 2
The treatment process is the same as example 1, except that: the temperature of the low-temperature freezing treatment is 0 ℃; the COD removal rate is about 95.5 percent through detection.
Example 3
The treatment process is the same as example 1, except that: the temperature of the low-temperature freezing treatment is 10 ℃; the COD removal rate is about 94.2 percent through detection.
Example 4
The treatment process is the same as example 1, except that: electrolyzing for 2 hours under the current of 5A; the COD removal rate is about 95.7 percent through detection.
Example 5
The treatment process is the same as example 1, except that: electrolyzing for 2 hours under the current of 1A; the COD removal rate is about 94.1 percent through detection.
Example 6
The treatment process is the same as example 1, except that: adjusting the pH value of the electrolytic wastewater to 4 by adopting sulfuric acid; the COD removal rate is about 93.9 percent through detection.
Example 7
The treatment process is the same as example 1, except that: electrolyzing for 30min under the current of 1A; the COD removal rate is about 92.7 percent through detection.
Example 8
The treatment process is the same as example 1, except that: the temperature of the low-temperature freezing treatment is 15 ℃; the COD removal rate is about 93.1 percent through detection.
Comparative example 1
High salt and COD wastewater treatment, Na2SO4The concentration is close to saturation, the mass concentration is 30 percent, and the COD concentration is about 30000 mg/L. First, low-temperature freezing treatment is carried out at 18 ℃ to make Na2SO4Crystallizing to obtain Natrii sulfas; filtering to obtain solid salt and pretreated wastewater; then, feeding the pretreated wastewater into an electrolytic cell, and electrolyzing for 1h under the condition that the current is 0.5A to obtain electrolytic wastewater; regulating the pH value of the electrolytic wastewater to 4.5 by adopting sulfuric acid, and standing for 10min to obtain acid-regulated wastewater; and finally, carrying out physical adsorption and decoloration on the acid-exchange wastewater by using active carbon, adsorbing the separated organic matters, and carrying out final decoloration treatment. The detection shows that the removal rate of COD is about 92.1 percent
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A treatment method of high-salt high-COD wastewater contains Na with a mass concentration of 30-40%2SO4And the COD value is 10000-30000 mg/L, and the treatment method is characterized by comprising the following steps:
s1, performing low-temperature freezing treatment on the high-salt high-COD wastewater at the treatment temperature of-5-10 ℃ to obtain a solid phase and pretreated wastewater;
s2, electrolyzing the pretreated wastewater to obtain electrolytic wastewater;
s3, adjusting the pH value of the electrolytic wastewater to 2.0-4.0 to separate out organic matters in the electrolytic wastewater to obtain acid-adjusting wastewater;
s4, carrying out physical adsorption and decoloration on the acid-regulated wastewater to obtain treated wastewater.
2. The method according to claim 1, wherein the temperature of the low-temperature freezing treatment in step S1 is 0 to 10 ℃.
3. The treatment method according to claim 1, wherein in the step S2, in the electrolysis of the pretreated wastewater, the electrolysis current is 1-5A, and the electrolysis time is 60-120 min.
4. The treatment method according to any one of claims 1 to 3, wherein the pH value of the high-salt high-COD wastewater is 5.0 to 10.0; preferably, in the step S4, the activated carbon is used to perform the physical adsorption and the decolorization on the acid-adjusted wastewater.
5. The treatment method according to any one of claims 1 to 3, wherein in the step S3, the pH value of the electrolytic wastewater is adjusted with sulfuric acid.
6. The treatment method according to any one of claims 1 to 3, wherein in the step S2, in the process of electrolyzing the pretreated wastewater, an electrolysis electrode is adopted, and preferably the material of the electrolysis electrode comprises titanium and alloy elements, and the alloy elements are one or more of platinum, ruthenium, iridium, lead and tin.
7. A treatment device for high-salt high-COD wastewater contains Na with the mass concentration of 30-40%2SO4And the COD value is 10000 ~ 30000mg/L, its characterized in that, the processing apparatus includes:
the low-temperature freezing unit (10) is used for performing low-temperature freezing treatment on the high-salt high-COD wastewater at the temperature of-5-10 ℃ to obtain pretreated wastewater;
the electrolysis unit (20) is connected with the low-temperature freezing unit (10) and is used for carrying out electrolysis treatment on the pretreated wastewater to obtain electrolytic wastewater;
the acid regulating unit (30) is connected with the electrolysis unit (20) and is used for regulating the pH value of the electrolysis wastewater to 2.0-4.0 to obtain acid regulating wastewater;
and the physical adsorption and decoloration unit (40) is connected with the acid regulating unit (30) and is used for carrying out physical adsorption and decoloration treatment on the acid regulating wastewater.
8. The treatment plant according to claim 7, characterized in that the electrolysis unit (20) comprises an electrolysis cell and electrolysis electrodes located in the electrolysis cell, the electrolysis electrodes being of a titanium alloy material, preferably the material of the electrolysis electrodes comprises titanium and an alloying element being one or more of platinum, ruthenium, iridium, lead, tin.
9. The treatment plant according to claim 7, characterized in that said physical adsorption and decolorization treatment is carried out in said physical adsorption and decolorization unit (40) using activated carbon.
10. The treatment plant according to claim 7, characterized in that said cryogenic freezing unit (10) comprises a cryogenic freezing device and a filtering device arranged in series with each other, said cryogenic freezing device being adapted to perform said cryogenic freezing treatment, said filtering device being adapted to filter the products of said cryogenic freezing treatment to obtain said pre-treated wastewater.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2395946A (en) * | 2002-12-05 | 2004-06-09 | Thomas Altmann | Extracting sodium chloride from seawater, using nanofiltration |
| CN204569619U (en) * | 2015-02-12 | 2015-08-19 | 重庆安欣环保节能科技有限公司 | Well-drilling waste water treatment unit |
| CN110697955A (en) * | 2019-10-11 | 2020-01-17 | 厦门嘉戎技术股份有限公司 | Nanofiltration concentrated solution treatment device and method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2395946A (en) * | 2002-12-05 | 2004-06-09 | Thomas Altmann | Extracting sodium chloride from seawater, using nanofiltration |
| CN204569619U (en) * | 2015-02-12 | 2015-08-19 | 重庆安欣环保节能科技有限公司 | Well-drilling waste water treatment unit |
| CN110697955A (en) * | 2019-10-11 | 2020-01-17 | 厦门嘉戎技术股份有限公司 | Nanofiltration concentrated solution treatment device and method |
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