CN111039504A - CBZ-containing underground water in-situ remediation method - Google Patents
CBZ-containing underground water in-situ remediation method Download PDFInfo
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- CN111039504A CN111039504A CN201911351928.3A CN201911351928A CN111039504A CN 111039504 A CN111039504 A CN 111039504A CN 201911351928 A CN201911351928 A CN 201911351928A CN 111039504 A CN111039504 A CN 111039504A
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- cbz
- sulfate
- carbamazepine
- situ remediation
- remediation method
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention discloses an in-situ remediation method for underground water containing CBZ, and relates to the field of underground water treatment. The invention aims to solve the problem that the existing peroxydisulfate degrades carbamazepine to generate secondary pollution (sulfate radical (SO)4 2‑) To develop a more efficient, economical, green and environmentally friendly process. The method reduces sulfate radical (SO) generated by degrading Carbamazepine (CBZ) by using Sulfate Reducing Bacteria (SRB) for the first time4 2‑) Oxidizing the Masipine (CBZ) in groundwater using sulfate radicals generated by peroxydisulfate activation, and reusing sulfateReduction of original bacteria (SRB) to remove sulfate radical (SO)4 2‑). Use of this method for Carbamazepine (CBZ) degradation and Sulfate (SO)4 2‑) The removal effect is obvious, and the degradation rate of CBZ and SO can be achieved within 114 hours4 2‑The removal rate of the catalyst can reach about 100 percent and 95 percent respectively. The method has the advantages of high pollutant removal rate, convenient operation and the like.
Description
Technical Field
The invention relates to the technical field of groundwater pollution control, in particular to in-situ remediation of groundwater containing CBZ.
Background
Pharmaceuticals and Personal Care Products (PPCPs) are an emerging class of micropollutants including antibiotics, prescription and over-the-counter drugs, fragrances, hygiene Products, supplements, and skin Care Products. Has the characteristics of low concentration, diversity, difficult volatilization, slow biodegradation and the like. The entry of such contaminants into the environment can be a serious threat to human health, and the risk of PPCPs is therefore of considerable value.
Carbamazepine is a typical PPCPs substance with an average annual consumption of 1014t worldwide. Because of the difficult degradation and durability of carbamazepine, the presence of carbamazepine is often detected in the detection of drug content in various aqueous solutions. Because carbamazepine is widely used, toxic and side effects are gradually concerned by people. Common side effects include lethargy, vomiting, constipation, etc., and serious side effects include decreased skin rash and bone marrow function, suicide impulsion, and confusion, and patients taking carbamazepine may also present a safety risk of causing skin reactions. Therefore, it cannot be effectively removed by the conventional process due to its difficult degradability and integrability.
Based on hydroxyl radicals (. OH) and sulfate radicals (SO)4 -·) has great potential in the removal of carbamazepine and has been widely used in wastewater and groundwater treatment. The advanced oxidation technology (Fenton oxidation technology) based on hydroxyl free radical (. OH) is commonCan be carried out under the normal conditions (normal temperature and normal pressure), and has the advantages of low reagent cost, easy storage, easy operation, safety and high efficiency. However, the traditional Fenton also has a plurality of defects: (1) the pH requirement on a reaction system is high; (2) generating ferric salt sludge; (3) h2O2Reaction with OH produces by-products and the like. Compared with OH, the advanced oxidation technology based on sulfate radicals (such as persulfate oxidation technology) has the advantages that: 1) SO (SO)4 -The capability of oxidizing and degrading pollutants is equivalent to or even stronger than that of OH, and the efficiency is higher and more thorough; 2) SO (SO)4 -Stability is stronger than. OH; 3) SO (SO)4 -Less influenced by external conditions than OH. The product of sulfate radical oxidation of carbamazepine is SO4 2-And SO4 2-The sulfate radical is widely present in water, a small amount of sulfate radical has no influence on human health, but when the concentration of the sulfate radical exceeds 250mg/L, the sulfate radical has a laxative effect on human bodies, and when the mass concentration of the calcium sulfate and the magnesium sulfate in the water respectively reaches 1000mg/L and 850mg/L, half of people think that the taste of the water is unpleasant and cannot accept the taste.
Disclosure of Invention
The invention aims to solve the technical problem that the prior art adopts the advanced oxidation technology of sulfate radical to remove carbamazepine to generate more SO4 2-And the technical problem of influencing water quality.
In order to solve the technical problems, the invention adopts the technical scheme that: an in-situ remediation method for underground water containing CBZ comprises the following steps:
(1) adding peroxydisulfate to underground water containing carbamazepine;
(2) heating the mixed solution to degrade carbamazepine;
(3) adding nutrient substances required by sulfate reducing bacteria culture into the degraded solution, adjusting the pH value of the solution, introducing nitrogen, then carrying out high-pressure high-temperature sterilization, and finally carrying out strain inoculation of SRB;
(4) method for removing SO by culturing sulfate reducing bacteria in constant temperature environment4 2-。
Further, the pH value of the mixture of underground water containing carbamazepine and peroxodisulfate is 6.0-8.0.
Further, underground water containing carbamazepine and mixed waste liquid of disulfate are heated by a constant temperature water bath shaking table, the temperature is controlled to be 55-60 ℃, and the shaking speed of the shaking table is 50-150 rpm.
Furthermore, the peroxodisulfate is one or a mixture of two of sodium peroxodisulfate and potassium peroxodisulfate mixed according to any proportion, and the concentration of the peroxodisulfate is controlled to be about 0.3-0.7 g/L.
Further, the mass ratio of the main components of nutrient substances required by the culture of the sulfate reducing bacteria is as follows: 1.5-2 parts of magnesium sulfate MgSO4, 4-6 parts of sodium citrate, 0.5-1.5 parts of calcium sulfate CaSO 4.2H2O, 0.5-1.5 parts of ammonia chloride NH4Cl, and 0.4-0.6 part of dipotassium hydrogen phosphate K2HPO43-4 parts of sodium lactate and 0.5-1.5 parts of yeast extract, wherein the concentration of MgSO4 in the culture solution is 1.5-2.5 g/L; further, the introduction time of nitrogen lasts for 10-15min, and the autoclaving conditions are as follows: 115 ℃ and 200 ℃, the pressure is 0.1-0.69MPa, and the sterilization time is 30-60 min.
Further, the sulfate reducing bacteria are desulfurization subspecies of desulfurization vibrio.
Furthermore, the temperature for culturing the sulfate-reducing bacteria is 35 ℃ and the culture time is about 5-7 day.
The technical scheme shows that the invention has the following advantages: the invention provides a method for degrading carbamazepine by combining peroxydisulfate and sulfate reducing bacteria, which not only obtains the high-efficiency and quick degradation effect of carbamazepine, but also removes sulfate ions of the carbamazepine degraded by peroxydisulfate. Promotes the popularization and the application of the new persulfate technology in the aspect of wastewater (liquid) treatment.
Drawings
FIG. 1 shows the process on carbamazepine and SO4 2-Schematic diagram of degradation effect of (1);
Detailed Description
The present invention will be described in detail with reference to the following examples and fig. 1. The scope of protection of the invention is not, however, limited to the examples listed below.
Example 1:
to 100mL of carbamazepine wastewater having a concentration of 1mg/L, 50mg of sodium peroxodisulfate was added to obtain a wastewater solution. The reaction is carried out for 24 hours in a constant temperature water bath shaker (60 ℃). Adding sulfate reducing bacteria culture reagent, adjusting pH of the solution to 7.5, introducing nitrogen for 15min, and autoclaving at 150 deg.C under 0.5MPa for 50 min.
Inoculating sulfate reducing bacteria into the solution after sterilization, wherein the nutrient substances required by the culture of the sulfate reducing bacteria comprise: magnesium sulfate (MgSO)4)2.0g, sodium citrate 5.0g, calcium sulfate (CaSO)4·2H2O)1.0g, ammonium chloride (NH)4Cl)1.0g, dipotassium hydrogen phosphate (K)2HPO4)0.5g, 3.5g of sodium lactate, 1.0g of yeast extract and 2.0 g/L of culture solution (MgSO 24For example);
the inoculated solution is placed in a constant-temperature (35 ℃) culture room for culture. As can be seen, the removal rate of the system (114 hours) to the carbamazepine reaches 100 percent; the removal rate of sulfate radicals is 99.05 percent. Example 2:
to 100mL of carbamazepine wastewater having a concentration of 5mg/L, 50mg of sodium peroxodisulfate was added to obtain a wastewater solution. The reaction is carried out for 24 hours in a constant temperature water bath shaker (60 ℃). Adding sulfate reducing bacteria culture reagent, adjusting pH of the solution to 7.5, introducing nitrogen for 15min, and autoclaving at 150 deg.C under 0.5MPa for 50 min.
Inoculating sulfate reducing bacteria into the solution after sterilization, wherein the nutrient substances required by the culture of the sulfate reducing bacteria comprise: magnesium sulfate (MgSO)4)1.9g, sodium citrate 5.0g, calcium sulfate (CaSO)4·2H2O)1.0g, ammonium chloride (NH)4Cl)1.0g, dipotassium hydrogen phosphate (K)2HPO4)0.5g, sodium lactate 3.5g and yeast extract 1.0 g;
the inoculated solution is placed in a constant-temperature (35 ℃) culture room for culture. As can be seen, the removal rate of the system (114 hours) to the carbamazepine reaches 100 percent; the removal rate of sulfate radicals was 85.89%.
Example 3:
to 100mL of carbamazepine wastewater having a concentration of 10mg/L, 50mg of sodium peroxodisulfate was added to obtain a wastewater solution. The reaction is carried out for 24 hours in a constant temperature water bath shaker (60 ℃). Adding sulfate reducing bacteria culture reagent, adjusting pH of the solution to 7.5, introducing nitrogen for 15min, and autoclaving at 150 deg.C under 0.5MPa for 50 min.
Inoculating sulfate reducing bacteria into the solution after sterilization, wherein the nutrient substances required by the culture of the sulfate reducing bacteria comprise: magnesium sulfate (MgSO)4)2.1g, sodium citrate 5.0g, calcium sulfate (CaSO)4·2H2O)1.0g, ammonium chloride (NH)4Cl)1.0g, dipotassium hydrogen phosphate (K)2HPO4)0.5g, sodium lactate 3.5g and yeast extract 1.0 g;
the inoculated solution is placed in a constant-temperature (35 ℃) culture room for culture. As can be seen, the removal rate of the system (114 hours) to the carbamazepine reaches 100 percent; the removal rate of sulfate radicals was 85.89%.
Claims (8)
1. An in-situ remediation method for underground water containing CBZ is characterized by comprising the following steps:
(1) adding peroxydisulfate to underground water containing carbamazepine;
(2) heating the mixed solution to degrade carbamazepine;
(3) adding nutrient substances required by sulfate reducing bacteria culture into the degraded solution, adjusting the pH value of the solution, introducing nitrogen, then carrying out high-pressure high-temperature sterilization, and finally carrying out strain inoculation of SRB;
(4) method for removing SO by culturing sulfate reducing bacteria in constant temperature environment4 2-。
2. The in situ remediation method of CBZ-containing groundwater according to claim 1, wherein: the pH value of the mixture of carbamazepine and peroxydisulfate is 6.0-8.0.
3. The in situ remediation method of CBZ-containing groundwater according to claim 1, wherein: heating underground water containing carbamazepine and mixed waste liquid of disulfate by using a constant-temperature water bath shaking table, controlling the temperature at 55-60 ℃, and controlling the shaking speed of the shaking table at 50-150 rpm.
4. The in situ remediation method of CBZ-containing groundwater according to claim 1, wherein: the peroxodisulfate is one or two of sodium peroxodisulfate and potassium peroxodisulfate mixed in any proportion, and the concentration of peroxodisulfate is controlled at about 0.3-0.7 g/L.
5. The in situ remediation method of CBZ-containing groundwater according to claim 1, wherein: the main components of nutrient substances required by the culture of the sulfate reducing bacteria are as follows: 1.5-2 parts of magnesium sulfate (MgSO)44-6 parts of sodium citrate and 0.5-1.5 parts of calcium sulfate CaSO4·2H2O, 0.5-1.5 parts of ammonium chloride NH4Cl and 0.4-0.6 part of dipotassium hydrogen phosphate K2HPO43-4 parts of sodium lactate, 0.5-1.5 parts of yeast extract and MgSO (MgSO) in culture solution4The concentration is 1.5-2.5 g/L.
6. The in situ remediation method of CBZ-containing groundwater according to claim 1, wherein: the nitrogen gas is introduced for 10-15min, and the autoclaving conditions are as follows: 115 ℃ and 200 ℃, the pressure is 0.1-0.69MPa, and the sterilization time is 30-60 min.
7. The in situ remediation method of CBZ-containing groundwater according to claim 1, wherein: the sulfate reducing bacteria are desulfurization subspecies of desulfurization vibrio.
8. The in situ remediation method of CBZ-containing groundwater according to claim 1, wherein: the temperature for culturing the sulfate reducing bacteria is 35 ℃, and the culture time is about 5-7 day.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2814399A1 (en) * | 2010-10-15 | 2012-04-19 | Hector Alvarez-Vazquez | Treatment of a waste stream through production and utilization of oxyhydrogen gas |
| CN105152239A (en) * | 2015-09-06 | 2015-12-16 | 同济大学 | Device and method for repairing underground water through process of activating sodium persulfate by using Fe (II) |
| CN107138520A (en) * | 2017-05-02 | 2017-09-08 | 东华理工大学 | The processing method of uranium contaminated soil is repaired in a kind of utilization sulfate Mixed Microbes reduction |
| CN109019822A (en) * | 2018-08-07 | 2018-12-18 | 北京伦至环境科技有限公司 | A kind of Organic Chemicals In Groundwater in-situ remediation method |
-
2019
- 2019-12-25 CN CN201911351928.3A patent/CN111039504A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2814399A1 (en) * | 2010-10-15 | 2012-04-19 | Hector Alvarez-Vazquez | Treatment of a waste stream through production and utilization of oxyhydrogen gas |
| CN105152239A (en) * | 2015-09-06 | 2015-12-16 | 同济大学 | Device and method for repairing underground water through process of activating sodium persulfate by using Fe (II) |
| CN107138520A (en) * | 2017-05-02 | 2017-09-08 | 东华理工大学 | The processing method of uranium contaminated soil is repaired in a kind of utilization sulfate Mixed Microbes reduction |
| CN109019822A (en) * | 2018-08-07 | 2018-12-18 | 北京伦至环境科技有限公司 | A kind of Organic Chemicals In Groundwater in-situ remediation method |
Non-Patent Citations (4)
| Title |
|---|
| 尧品华等编著: "《厌氧环境试验微生物》", 30 June 2015, 哈尔滨工业大学出版社 * |
| 张敬慧主编: "《酿酒微生物》", 31 January 2015, 中国轻工业出版社 * |
| 杨照荣: "热激活过硫酸盐氧化典型PPCPs污染物的机理研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑（月刊）》 * |
| 罗进: "活化过硫酸盐氧化修复柴油污染土壤研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑（月刊）》 * |
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