CN113003792A - Treatment method of high-salt organic wastewater containing quinolinic acids - Google Patents
Treatment method of high-salt organic wastewater containing quinolinic acids Download PDFInfo
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- CN113003792A CN113003792A CN202110414749.0A CN202110414749A CN113003792A CN 113003792 A CN113003792 A CN 113003792A CN 202110414749 A CN202110414749 A CN 202110414749A CN 113003792 A CN113003792 A CN 113003792A
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F1/66—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
- C02F2101/20—Heavy metals or heavy metal 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
- C02F2101/30—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
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a method for treating high-salt organic wastewater containing quinolinic acids, and belongs to the field of water treatment. Comprises the following steps of 1) adding alkali and heating wastewater generated in the production of quinline acid for pretreatment, 2) flowing through copper-removing resin for copper adsorption treatment, and 3) finally carrying out organic matter adsorption treatment on the wastewater through styrene series ultrahigh cross-linked resin. By combining the oxidation process and the resin adsorption process of copper ions and organic matters, the invention can separate the Cu ions and the organic matters in the wastewater, can also effectively treat the regenerated liquid generated in the resin regeneration process, and improves the salt production quality of the wastewater.
Description
The invention belongs to the field of wastewater recycling, and particularly relates to a method for treating high-salt organic wastewater containing quinolinic acids.
Background
At present, in the rapid development of the chemical industry, the quantity and the types of the wastewater generated in the production process gradually tend to be diversified, and the impact on the ecological environment is gradually deepened. In particular to high-salt organic wastewater generated in the production process of pesticides. Due to the ultrahigh salt content in the water body, the growth of most microorganisms is inhibited, so that the biochemical process is difficult to touch the field of high-salt wastewater; the chemical method is not favorable for salt recovery because new ions are easily introduced due to the need of adding chemicals. Therefore, an electrochemical process, a membrane process, an oxidation process, an adsorption process and the like are often adopted in the field of organic high-salt wastewater, if the electrochemical process is adopted, the situation that the electric energy consumption of the wastewater is too high in the treatment process and the electrode is passivated in the continuous use process can occur, and the operation cost of wastewater treatment is greatly increased; the membrane process can isolate organic matters in wastewater, but membrane pollution and difficulty in treating concentrated solution occur over time. Although the chemical oxidation method can degrade organic matters in the wastewater, the problem of high operation cost still exists due to the addition of large amount of medicament, the treatment of high-concentration desorption is often difficult to solve when a resin adsorption process is adopted, and in the high-salt organic wastewater of the quinolinic acid, the high-concentration desorption solution can be put into production again, so that the recycling of the wastewater desorption solution is realized.
Against Cu in wastewater2+In this case, a method of adding quicklime for precipitation is generally used, although it is possible to largely remove Cu in wastewater2+However, it is difficult to achieve the effect of advanced treatment, and Cu in wastewater cannot be completely removed2+The quality of the salt is ultimately affected. By adopting the sodium sulfide precipitation method, a large amount of hydrogen sulfide gas can be generated in the reaction process, so that air pollution can be caused, and the health and safety of operators can be threatened. By adopting a resin adsorption method, the Cu in the wastewater can be deeply treated2+The water treatment device adsorbs pollutants in the wastewater, is not influenced by the salt content in the wastewater, reduces the content of organic matters in the wastewater, adsorbs polymer organic matters which are difficult to biochemistry in the wastewater, thereby achieving the effect of decoloring the wastewater and improving the quality of evaporating salt.
Disclosure of Invention
Technical problem to be solved by the invention
Aiming at the problems that the content of copper ions and organic matters in the quinolinic acid wastewater is high and salt cannot be recovered, the invention provides a method for treating high-salt organic wastewater containing quinolinic acid. Two kinds of resin desorption liquid are obtained and are mixed to return to the production section again, thereby realizing good wastewater treatment effect and economic benefit.
Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a method for treating high-salt organic wastewater containing quinolinic acids, which comprises a wastewater pretreatment step, a copper-removing resin adsorption step and a styrene series ultrahigh cross-linked resin adsorption step.
Preferably, the alkali solution in the pretreatment step is one or more of a KOH solution, a NaOH solution, ammonia water or lime.
Preferably, the volume total exchange capacity of the copper-removing resin adopted in the copper-removing resin adsorption step is more than or equal to 1.2mmol/ml, and the sphericity rate after grinding is 85-99%.
Preferably, the specific surface area of the styrene-based ultrahigh crosslinked resin adopted in the adsorption step of the styrene-based ultrahigh crosslinked resin is 800-1400 m2The sphericity ratio after grinding is 80-99%, and the average pore diameter is 2.8-3.4 nm.
Preferably, the copper-removing resin is filled in the primary resin adsorption column, and the height-diameter ratio of the filling is 3: 1-5: 1; the styrene series ultrahigh crosslinked resin is filled in a secondary resin adsorption column, and the ratio of height to diameter of the filled resin is 3: 1-5: 1.
preferably, the flow rate of the wastewater flowing through the phosphoramidate resin in the copper removal resin adsorption step is 0.5-10BV/h, and the wastewater adsorption volume is 10-100 BV.
Preferably, the flow rate of the wastewater flowing through the resin in the step of adsorbing the styrene-based ultrahigh cross-linked resin is 0.5-5BV/h, and the adsorption volume of the wastewater is 10-50 BV.
Preferably, in the step of regenerating the copper-removed resin adsorbent, 1-5% dilute hydrochloric acid or dilute sulfuric acid can be selected as the regeneration liquid, the using amount of the regeneration liquid is 2-6BV, and the regeneration flow rate is 0.5-1 BV/h.
Preferably, in the step of regenerating the styrene series ultrahigh crosslinked resin, 2-10% NaOH is selected as the regenerating liquid, the using amount of the regenerating liquid is 2-6BV, the temperature of the regenerating liquid is 40-60 ℃, and the regenerating flow rate is 0.5-1 BV/h.
Preferably, the copper-removing resin regenerated liquid and the styrene-based ultrahigh crosslinked resin regenerated liquid are mixed and then return to the production process.
Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for treating the high-salt organic wastewater containing the quinolinic acids, the treatment process taking the resin adsorption technology as a core is adopted, the copper-removing resin and the styrene series ultrahigh cross-linked resin are effectively combined, copper and organic matters in the wastewater can be effectively removed, and the salt distilled from the resin effluent has a recycling value;
(2) according to the method for treating the high-salt organic wastewater containing the quinolinic acid, the resin adsorption is used as a core treatment process, when the two kinds of resins are saturated in adsorption, dilute acid and dilute alkali are respectively adopted for regeneration, the two kinds of desorbents are mixed to obtain high-concentration quinolinic acid and copper salt, and the quinolinic acid and the copper salt are returned to a production working section again to obtain effective recycling;
example 1
The wastewater of the embodiment, the wastewater of the quinolinic acid oxidation section of a certain chemical industry enterprise, contains 560mg/L of copper ions and 4549mg/L of TOC.
The method for treating high-salt organic wastewater containing quinolinic acids comprises the following steps:
(1) adjusting the pH value of the wastewater to 9-10 by using 30% liquid caustic soda, and then flowing the wastewater through a bag type filtering device to remove mechanical impurities, wherein the copper ion content in the wastewater is 220mg/L, and the TOC3951 mg/L.
(2) And (2) sending the wastewater filtered in the step (1) into a copper-removing resin adsorption tower for treatment, adsorbing copper ions in the wastewater, wherein the content of the copper ions in resin effluent is 0.46mg/L, and the TOC3951 mg/L. (ii) a
(3) And (3) sending the resin effluent in the step (2) into a styrene series ultrahigh cross-linked resin tower for adsorption treatment to adsorb organic matters in the wastewater, wherein the TOC220mg/L of the resin effluent at the moment has an organic matter removal rate of about 94.4%.
Claims (10)
1. A method for treating high-salt organic wastewater containing quinolinic acids is characterized by comprising the following steps:
pretreatment: firstly, adding alkali liquor into the wastewater to be treated to ensure that the pH of the wastewater is 8-12 and the reaction time is 0.5-2 h;
copper ion adsorption: enabling the wastewater filtered in the step (1) to flow through copper-removing resin for adsorption treatment;
organic matter adsorption: and (3) allowing the wastewater subjected to the step (2) to flow through styrene series ultrahigh cross-linked resin for adsorption treatment.
2. The method for treating high-salt organic wastewater containing quinolinic acids as claimed in claim 1, wherein the alkali solution in step 1 is one or more of KOH solution, NaOH solution, ammonia water or lime.
3. The method for treating high-salt organic wastewater containing quinolinic acids as in claim 1, wherein the volume total exchange capacity of the copper-removing resin adopted in the step (2) is not less than 1.2mmol/ml, and the sphericity after grinding is 85% -99%.
4. The method for treating high-salt organic wastewater containing quinolinic acids as claimed in claim 1, wherein the specific surface area of the styrene-based ultrahigh cross-linked resin adopted in the resin adsorption step 3 is 800-1400 m2The sphericity ratio after grinding is 80-99%, and the average pore diameter is 2.8-3.4 nm.
5. The method for treating high-salt organic wastewater containing quinolinic acids as in claim 1, wherein the copper-removing resin is filled in the primary resin adsorption column, and the ratio of the filled height to diameter is 3: 1-5: 1; the styrene series ultrahigh crosslinked resin is filled in a secondary resin adsorption column, and the ratio of height to diameter of the filled resin is 3: 1-5: 1.
6. the method for treating high-salt organic wastewater containing quinolinic acids as in claim 1, wherein the flow rate of wastewater flowing through the phosphoramidate resin in step 2 is 0.5-10BV/h, and the adsorption volume of wastewater is 10-100 BV.
7. The method for treating high-salt organic wastewater containing quinolinic acids as in claim 1, wherein the flow rate of wastewater flowing through the styrene-based ultra-high crosslinked resin in step 3 is 0.5-5BV/h, and the adsorption volume of wastewater is 10-50 BV.
8. The method for treating high-salt organic wastewater containing quinolinic acids as in claim 1, wherein in the step of regenerating resin in step 2, the regenerating solution is selected from 1-5% dilute hydrochloric acid or dilute sulfuric acid, the using amount of the regenerating solution is 2-6BV, and the regenerating flow rate is 0.5-1 BV/h.
9. The method for treating high-salt organic wastewater containing quinolinic acids as in claim 1, wherein in the step of regenerating resin in step 3, 2-10% NaOH is selected as the regenerating liquid, the using amount of the regenerating liquid is 2-6BV, the temperature of the regenerating liquid is 40-60 ℃, and the regenerating flow rate is 0.5-1 BV/h.
10. The method for treating high-salt organic wastewater containing quinolinic acids as in claim 1, wherein the regenerated liquid from step 8 and step 9 is mixed and returned to production.
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| CN202110414749.0A CN113003792A (en) | 2021-04-17 | 2021-04-17 | Treatment method of high-salt organic wastewater containing quinolinic acids |
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| CN202110414749.0A CN113003792A (en) | 2021-04-17 | 2021-04-17 | Treatment method of high-salt organic wastewater containing quinolinic acids |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88103282A (en) * | 1987-06-02 | 1988-12-21 | 皮奇尼铅公司 | The method of extraction and gallium-purifying from Bayer-liquid |
| JP2018034095A (en) * | 2016-08-30 | 2018-03-08 | 月島環境エンジニアリング株式会社 | Method for regenerating cation exchange resin, method for treating liquid to be treated, and treatment facility containing cation exchange resin |
| CN109912096A (en) * | 2019-03-11 | 2019-06-21 | 江苏南大华兴环保科技股份公司 | A kind of pretreated method of o-methyl formate benzene sulfonamide waste water sub-prime |
| CN112645489A (en) * | 2020-12-07 | 2021-04-13 | 江苏国创新材料研究中心有限公司 | High-salinity wastewater treatment method based on adsorption and oxidation of temperature swing desorption resin |
-
2021
- 2021-04-17 CN CN202110414749.0A patent/CN113003792A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88103282A (en) * | 1987-06-02 | 1988-12-21 | 皮奇尼铅公司 | The method of extraction and gallium-purifying from Bayer-liquid |
| JP2018034095A (en) * | 2016-08-30 | 2018-03-08 | 月島環境エンジニアリング株式会社 | Method for regenerating cation exchange resin, method for treating liquid to be treated, and treatment facility containing cation exchange resin |
| CN109912096A (en) * | 2019-03-11 | 2019-06-21 | 江苏南大华兴环保科技股份公司 | A kind of pretreated method of o-methyl formate benzene sulfonamide waste water sub-prime |
| CN112645489A (en) * | 2020-12-07 | 2021-04-13 | 江苏国创新材料研究中心有限公司 | High-salinity wastewater treatment method based on adsorption and oxidation of temperature swing desorption resin |
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Application publication date: 20210622 |