CN113003820B - Method for treating halogenated organic matter wastewater by virtue of advanced reduction-oxidation coupling system based on semi-dry flue gas desulfurization ash - Google Patents
Method for treating halogenated organic matter wastewater by virtue of advanced reduction-oxidation coupling system based on semi-dry flue gas desulfurization ash Download PDFInfo
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- 239000013543 active substance Substances 0.000 claims description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 claims description 2
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- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 230000001502 supplementing effect Effects 0.000 claims 1
- -1 hydrogen free radical Chemical class 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 4
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- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 206010021143 Hypoxia Diseases 0.000 abstract description 2
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
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- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention belongs to the technical field of solid waste resource utilization and advanced oxidation-reduction treatment of wastewater, and particularly relates to a method for treating halogenated organic matter wastewater by using an advanced reduction-oxidation coupling system based on semidry flue gas desulfurization ash. The system utilizes ultraviolet light to release SO from semi-dry desulfurization ash 3 ‑ Activated under the condition of oxygen deficiency of the system to generate strong reducing hydrated electronse aq ‑ And hydrogen free radical H to destroy C-X bond of halogenated organic matter to realize reduction dehalogenation of halogenated organic matter; after the dehalogenation stage is finished, in-situ oxygen introduction (dissolved oxygen supplementation) is carried out, and SO released by desulfurized fly ash 3 ‑ With dissolved oxygen O 2 Under the activation of ultraviolet light, sulfate radical SO with strong oxidizing property is generated 4 ·‑ And the dehalogenated organic matters are further oxidized and decomposed into small molecular organic matters until the small molecular organic matters are mineralized, so that the biodegradability of the wastewater is improved, and the organic pollution load is reduced.
Description
Technical Field
The invention belongs to the technical field of solid waste resource utilization and wastewater advanced oxidation-reduction treatment, and particularly relates to a method for treating halogenated organic wastewater by using an advanced reduction-oxidation coupling system based on semidry flue gas desulfurization ash.
Background
Organic halides are often used as raw materials, intermediates, solvents and the like to be widely applied to organic synthesis, and have obvious effects in human production and life. The use and discharge of a large amount of halogenated organic matters cause the pollution of the halogenated matters in the water body to be increasingly serious, and threaten the ecological safety and the human health. Such as halogenated hydrocarbons, polychlorinated biphenyls, organochlorine pesticides, antibiotics and perfluorooctanesulfonic acid pollutants are representative of the persistent organic pollutants that are widely present in water. A great deal of research shows that the halogenated organic pollutants have the characteristics of environmental persistence, difficult biodegradation, bioaccumulation, high toxicity, long-distance migration capacity and the like, are distributed in the field environments such as soil, atmosphere and the like, and how to effectively solve the problem of halogenated pollutants becomes the concern in the field of environmentA focal point. The common halogenated organic matter treatment methods include adsorption method, incineration method, wet catalytic oxidation method, chemical reduction method for loading noble metals with hydrogen storage capacity, advanced oxidation and advanced reduction method, etc. Advanced reduction method can generate strong reducing hydrated electrons in systeme aq - And hydrogen free radical H breaks C-X bond to have strong dehalogenation effect, thereby breaking the structure of the halide and improving biodegradability. The advanced oxidation technology utilizes strong oxidizing radicals such as hydroxyl radical (OH) generated in the chemical reaction process · ) And sulfate radical (SO) 4 ·- ) And oxidizing and decomposing organic matters into small molecules through a series of chain reactions until the organic matters are degraded and mineralized. For halogenated organic matters, the organic matters can be degraded by an advanced oxidation method or an advanced reduction method, and compared with the advanced reduction method, the advanced reduction method has higher dehalogenation performance, and the advanced oxidation method has higher efficiency in the aspects of organic matter degradation and mineralization.
The semidry flue gas desulfurization technique is similar to the traditional wet lime-gypsum method in basic principle, and takes lime slurry as an absorbent to be fully contacted with the flue gas in an absorption tower, SO as to remove SO in the flue gas 2 And (4) absorbing. The desulfurization is accompanied with the particle drying process, so the desulfurization product is in a dry powder state, and no wastewater is generated. The semidry flue gas desulfurization ash contains a large amount of calcium sulfite, calcium carbonate and calcium oxide, has large component fluctuation, is strong in basicity and easy to decompose, and is very difficult to comprehensively utilize.
Disclosure of Invention
The invention provides a method for treating halogenated organic matter wastewater based on a high-grade reduction-oxidation coupling system of semi-dry flue gas desulfurization ash 3 - Activated under the condition of oxygen deficiency of the system to generate strong reducing hydrated electronse aq - And hydrogen free radical H to destroy C-X bond of halogenated organic matter to realize reduction dehalogenation of halogenated organic matter; after the dehalogenation stage is finished, in-situ oxygen introduction (dissolved oxygen supplementation) is carried out, and SO released by desulfurized fly ash 3 - With dissolved oxygen O 2 Under the activation of ultraviolet light, strong oxidizing sulfate radicals are generatedRadical SO 4 ·- And the dehalogenated organic matters are further oxidized and decomposed into small molecular organic matters until the small molecular organic matters are mineralized, so that the biodegradability of the wastewater is improved, and the organic pollution load is reduced. The method realizes high value-added resource utilization of wastes while performing harmless treatment on halogenated organic matters and desulfurized fly ash in the wastewater, achieves the aim of treating wastes with processes of wastes against one another, and has remarkable economic, social and environmental benefits.
1. A method for treating halogenated organic matter wastewater by using a high-grade reduction-oxidation coupling system based on semidry flue gas desulfurization ash comprises the following steps:
(1) Grinding waste residues generated by a semi-dry calcium method flue gas desulfurization system which operates stably and sieving by a 80-mesh sieve, and bagging the sieved powder for later use;
(2) Reduction and dehalogenation stage: placing a certain amount of halogenated organic matter wastewater into a reaction tank, adding a certain amount of desulfurized ash, and introducing nitrogen to remove dissolved oxygen in the system; adjusting pH =3.0-9.0, stirring continuously, and continuously irradiating for 15-180 min with low pressure mercury lamp (UVC band ultraviolet light);
(3) And (3) an oxidative decomposition stage: after the reduction dehalogenation stage is finished, continuously adding a certain amount of desulfurization ash and nano transition metal oxide catalyst into the wastewater, and slowly introducing air to increase dissolved oxygen; adjusting pH =5.0-9.0, stirring continuously, and continuously irradiating for 15-180 min with low pressure mercury lamp (UVC band ultraviolet light);
(4) Adjusting the pH of the treated wastewater to be 6.0-7.0, and filtering the effluent.
The semi-dry desulphurization ash is waste generated by a semi-dry calcium flue gas desulphurization system, and can realize the slow release of sulfite in the system.
The organic halide is an environmentally persistent organic pollutant containing halogen elements F, cl, br and I, such as halohydrocarbon, polychlorinated biphenyl, organochlorine pesticide, antibiotic and the like, and has stable property and difficult biodegradation.
The added desulfurized gray matter amount in the reduction dehalogenation stage is about 30-60 times of the organic halide amount, and the reaction pH =2.0-9.0.
In the reduction dehalogenation stage, a low-pressure mercury lamp is used as a light source (UVB band ultraviolet light), and the irradiation time is 15-120min.
The catalyst used in the oxidative decomposition stage is a nano-sized transition metal oxide such as TiO 2 ZnO and Fe 2 O 3 One or more of them.
The added desulfurized gray matter amount in the oxidative decomposition stage is about 10-40 times of the organic matter amount in the wastewater, and the reaction pH is controlled to be 5.0-9.0.
The light source in the oxidative decomposition stage adopts a low-pressure mercury lamp (UVB wave band ultraviolet light), and the continuous irradiation is carried out for 15-120min.
The advanced reduction-oxidation coupling system is based on active substances generated in the ultraviolet light activated desulfurization ash process, and realizes the in-situ switching of the advanced reduction process and the advanced oxidation process by controlling the dissolved oxygen content, the pH value and other conditions.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
the method has good effect of removing halogenated organic matters in the wastewater, realizes low-cost high-added-value utilization of the flue gas desulfurization waste, achieves the aim of treating the waste by the waste, and has remarkable economic benefit, social benefit and environmental benefit.
Drawings
FIG. 1 is a photograph of semi-dry desulfurized fly ash used in the examples of the invention.
FIG. 2 is an XRD pattern of semi-dry desulfurized fly ash used in the examples of the invention.
Detailed Description
The method and technique of the present invention are described below by way of example, but not limited thereto in practical applications.
Example 1
The method for treating the halogenated organic matter wastewater by using the advanced reduction-oxidation coupling system based on the semi-dry flue gas desulfurization ash comprises the following steps of:
(1) Grinding waste residues generated by a semi-dry calcium flue gas desulfurization system which operates stably and sieving the waste residues with a 80-mesh sieve, and bagging the sieved powder for later use;
(2) Reduction and dehalogenation stage: 500 mL of ciprofloxacin (C) with the concentration of 30 mg/L is taken 17 H 18 FN 3 O 3 ) Adding 0.4 g of desulfurized fly ash into the wastewater in a reaction tank, and introducing nitrogen to remove dissolved oxygen in the system after the wastewater is fully mixed; adjusting the pH of the system to be 5.0, continuously stirring, and continuously irradiating for 40min by adopting a UVC wave band low-pressure mercury lamp;
(3) And (3) an oxidative decomposition stage: after the reduction and dehalogenation stage is finished, 0.2g of desulfurized fly ash and 5mg of nano alpha-Fe are continuously added into the wastewater 2 O 3 Introducing air at 0.8L/min; adjusting the pH of the system to be 7.5, continuously stirring, and continuously irradiating for 120min by using a low-pressure mercury lamp (ultraviolet light with UVC wave band);
(4) Adjusting the pH of the treated wastewater to be 6.0-7.0, and filtering the effluent.
The defluorination rate of ciprofloxacin of the treated wastewater is determined to be more than 98 percent, and the mineralization rate of organic matters can reach 85 percent.
Example 2
The method for treating the halogenated organic matter wastewater by using the advanced reduction-oxidation coupling system based on the semi-dry flue gas desulfurization ash comprises the following steps of:
(1) Grinding waste residues generated by a semi-dry calcium flue gas desulfurization system which operates stably, sieving the waste residues through an 80-mesh sieve, and bagging the sieved powder for later use;
(2) A reduction dehalogenation stage: 500 mL of 50mg/L trichlorophenol (C) 6 H 3 Cl 3 O) adding 0.6 g of desulfurized fly ash into the wastewater in a reaction tank, and introducing nitrogen to remove dissolved oxygen in the system after fully mixing; adjusting the pH of the system to be 8.0, continuously stirring, and continuously irradiating for 100 min by using a low-pressure mercury lamp (ultraviolet light with UVC wave band);
(3) And (3) an oxidative decomposition stage: after the reduction dehalogenation stage is finished, 0.3 g of desulfurized fly ash and 6mg of nano TiO are continuously added into the wastewater 2 Introducing air at 0.8L/min; adjusting the pH of the system to be 7.0, continuously stirring, and continuously irradiating for 120min by using a low-pressure mercury lamp (ultraviolet light with UVC wave band);
(4) Adjusting the pH of the treated wastewater to be 6.0-7.0, and filtering the effluent.
The dechlorination rate of trichlorophenol in the treated wastewater is determined to be more than 98 percent, and the mineralization rate of organic matters can reach 90 percent
The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited thereto,
technical solutions according to the present invention and methods thereof within the technical scope of the present disclosure
The inventive concept is intended to cover such alternatives, modifications and variations as may be included within the spirit and scope of the invention.
Claims (6)
1. A method for treating halogenated organic matter wastewater by using a high-grade reduction-oxidation coupling system based on semidry flue gas desulfurization ash is characterized by comprising the following steps:
(1) Grinding desulfurization ash generated by a semi-dry calcium flue gas desulfurization system which operates stably and passing through a 80-mesh sieve, and bagging the desulfurization ash powder under the sieve for later use, wherein the desulfurization ash powder can realize slow release of sulfite in the system;
(2) Reduction and dehalogenation stage: placing a certain amount of halogenated organic matter wastewater into a reaction tank, adding a certain amount of desulfurized fly ash powder, and introducing nitrogen to remove dissolved oxygen in the system; adjusting the pH of the system to be 3.0-9.0, continuously stirring, and continuously irradiating for 15-180 min by adopting a UVC band low-pressure mercury lamp;
(3) And (3) an oxidative decomposition stage: after the reduction dehalogenation stage is finished, continuously supplementing a certain amount of desulfurized fly ash powder and nano transition metal oxide catalyst into the wastewater, and slowly introducing air to increase dissolved oxygen; adjusting the pH of the system to 5.0-9.0, continuously stirring, and continuously irradiating for 15-180 min by using a UVC band low-pressure mercury lamp;
(4) Adjusting the pH of the treated wastewater to be 6.0-7.0, and filtering the effluent.
2. The method for treating the halogenated organic matter wastewater by using the advanced reduction-oxidation coupling system based on the semidry flue gas desulfurization ash according to claim 1, wherein the halogenated organic matter is an environmentally persistent organic pollutant containing halogen elements F, cl, br and I, and is stable in property and difficult to biodegrade.
3. The method for treating the halogenated organic matter wastewater by using the advanced reduction-oxidation coupling system based on the semidry flue gas desulfurization ash according to claim 1, wherein the mass of desulfurization ash powder added in the reduction dehalogenation stage is 30-60 times of that of the halogenated organic matter in the wastewater.
4. The method for treating halogenated organic matter wastewater by using the advanced reduction-oxidation coupling system based on semidry flue gas desulfurization ash according to claim 1, wherein the catalyst used in the oxidative decomposition stage is nano-scale transition metal oxide TiO 2 ZnO and Fe 2 O 3 One or more of them.
5. The method for treating the halogenated organic matter wastewater by using the advanced reduction-oxidation coupling system based on the semidry flue gas desulfurization ash according to claim 1, wherein the mass of the supplemented desulfurization ash powder in the oxidative decomposition stage is 10-40 times of that of the halogenated organic matter in the wastewater.
6. The method for treating halogenated organic matter wastewater by using the advanced reduction-oxidation coupling system based on semidry flue gas desulfurization ash according to claim 1, wherein the advanced reduction-oxidation coupling system is based on active substances generated in the process of activating desulfurization ash by ultraviolet light, and the in-situ switching of the advanced reduction and advanced oxidation processes can be realized by controlling the content of dissolved oxygen and the pH value.
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