CN113830941A - Method for advanced treatment of organic wastewater by using micro-channel in cooperation with chlorine water and electron beam - Google Patents
Method for advanced treatment of organic wastewater by using micro-channel in cooperation with chlorine water and electron beam Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/305—Treatment of water, waste water, or sewage by irradiation with electrons
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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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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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
- C02F2209/11—Turbidity
Abstract
The invention provides a method for deeply treating organic wastewater by using micro-channels in cooperation with chlorine water and electron beams, which is characterized by comprising the following steps of: s1, introducing chlorine water and organic wastewater into the microchannel reactor to obtain intermediate liquid; s2, irradiating the interstitial fluid by using an electron beam, and adding a flocculating agent into the effluent for precipitation; s3, filtering the mixed solution obtained in the S2, adding a reducing agent, and obtaining reclaimed water with COD less than 50ppm and SS less than 10mg/L through an RO membrane; the mass ratio of the chlorine water to the organic wastewater in S1 is 1-30: 100. due to the synergistic effect of the microchannel reactor, the contact probability of effective chlorine and free chlorine with organic matters in the wastewater is increased, heat and mass transfer is enhanced, and the reaction efficiency and the oxidation efficiency are improved; the electron beam irradiation technology is used for replacing an oxidant, so that the high efficiency and automation of wastewater treatment are realized, the safety, environmental protection and cleanness of the wastewater treatment are realized, COD (chemical oxygen demand) in the treated wastewater is less than 50ppm, SS (suspended substance) is less than 20mg/L, the appearance is colorless and transparent, and the treated wastewater can be recycled as reclaimed water to realize the recycling of the water.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for deeply treating organic wastewater by using micro-channels in cooperation with chlorine water and electron beams.
Background
At present, in order to meet the demand of society on chemical products, the chemical industry of China is in the situation of high-speed development, a large amount of chemical wastewater is generated every day, the water quality of the wastewater increasingly shows the trends of complexity, high concentration, high toxicity, difficult degradation and the like, if the wastewater is not properly treated, the conditions of water body hypoxia and water quality reduction can be caused, and due to the long-term accumulation of harmful substances, the health of a human body can be affected even, and serious ecological problems are caused. Researchers have long been working on wastewater treatment processes in order to meet increasingly stringent wastewater discharge standards. The method for treating the wastewater mainly comprises a physical method, a biological method and a chemical method, wherein the physical method comprises a membrane separation method, an oil separation method, an air floatation method and an adsorption method; biological methods rely primarily on the decomposition of waste by anaerobic or aerobic microorganisms; the chemical method mainly refers to ozonization, chemical precipitation and flocculation.
Advanced oxidation technologies (AOPs) have become a research hotspot in the field of wastewater treatment in recent years due to the characteristics of strong oxidizing property, high treatment efficiency, wide application, no secondary pollution and the like. The method is mainly a technology for treating organic pollutants through strong oxidizing property of generated hydroxyl radicals, and the technology is mainly divided into ozone oxidation, photochemical oxidation, electrochemical oxidation, Fenton oxidation and the like. The microchannel reactor is popularized and applied in chemical production due to rapid reaction, high heat transfer and mass transfer efficiency and environmental friendliness. Through the synergistic effect of advanced oxidation technology and the micro-channel reactor, good effect can be obtained when the industrial wastewater is treated, and patent CN108773894B discloses a method for treating industrial wastewater by using the micro-channel reactorThe patent discloses a method and a device for continuously treating high-salt high-COD organic wastewater through deep catalytic oxidation, wherein a catalytic oxidation auxiliary agent is mixed into the high-salt high-COD organic wastewater in advance, the mixture enters a microchannel reactor through preheating, and is desalted through flash evaporation and evaporation concentration after undergoing an oxidation reaction with an oxidant, the removal rate of COD in the organic wastewater is more than 97.5%, and the salt content in solid salt is more than or equal to 98.5 wt%; cu2+Less than or equal to 2.0 mu g/g; TOC is less than or equal to 20.0 mu g/g. Patent CN113003852A discloses a method for realizing the economic and safe standard discharge of high-concentration refractory organic wastewater by combining ultrasonic, hydrogen peroxide and a micro-channel method, utilizing the ultrasonic to generate transient cavitation and stable cavitation, matching with the treatment of hydrogen peroxide and the micro-channel, and the catalytic decomposition of the ultrasonic to the hydrogen peroxide. Patent CN113003850A discloses a method for achieving up-to-standard discharge of organic waste water by advanced oxidation of refractory organic matters based on synergistic treatment of ultraviolet rays, ozone and micro-channels and matching with biochemical treatment of sewage in the advanced oxidation.
However, the above methods all require the addition of a large amount of oxidizing agents, and the recycling of wastewater cannot be realized, so how to form a wastewater treatment combined process with high efficiency and low energy consumption while reducing the addition amount of the oxidizing agents, find a green and friendly wastewater treatment path, and finally realize the reuse of reclaimed water is a problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a method for deeply treating organic wastewater by using micro-channels in cooperation with chlorine water and electron beams.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for deeply treating organic wastewater by using micro-channels in cooperation with chlorine water and electron beams comprises the following steps:
s1, introducing chlorine water and organic wastewater into the microchannel reactor to obtain intermediate liquid;
s2, irradiating the interstitial fluid by using an electron beam, and adding a flocculating agent into the effluent for precipitation;
s3, filtering the mixed solution obtained in the S2, adding a reducing agent, and obtaining reclaimed water with COD less than 50ppm and SS less than 10mg/L through an RO membrane;
the mass ratio of the chlorine water to the organic wastewater in S1 is 1-30: 100.
further, the electron beam irradiation dose is 1-15kGy, and the electron beam irradiation excites the intermediate liquid to generate strong oxidation particles to complete the oxidation reaction.
Further, the flocculant is any one of PSAA, PFSS, PAC and PSF, and the mass ratio of the flocculant to effluent is 0.005-0.05: 100.
Further, the reducing agent is any one of sodium sulfite and sodium bisulfite.
Furthermore, the dosage of the reducing agent is 10-1000mg/L, and the reaction time in S3 is 0.5-3 h.
Further, the reaction temperature in the S1 is 30-150 ℃, and the reaction residence time is 10-120S.
Furthermore, the COD of the organic wastewater is less than 1000ppm, the SS is less than 100mg/L, the turbidity is less than 300NTU, the pH value is 6-8, the color is reddish brown, and the characteristic pollutants are mainly heterocyclic organic matters such as pyridine rings and the like and derivatives thereof.
Further, the chlorine water is a byproduct in the production process of chlor-alkali, and the total content of free chlorine and available chlorine is 3000-10000 ppm.
Compared with the prior art, the invention has the beneficial effects that:
(1) due to the synergistic effect of the microchannel reactor, the contact probability of effective chlorine and free chlorine with organic matters in the wastewater is increased, the heat and mass transfer is enhanced, and the reaction efficiency and the oxidation efficiency are improved;
(2) the electron beam irradiation technology is used for replacing an oxidant, so that the high efficiency and automation of wastewater treatment are realized, the safety, environmental protection and cleanness of the wastewater treatment are realized, COD (chemical oxygen demand) in the treated wastewater is less than 50ppm, SS (suspended substance) is less than 20mg/L, the appearance is colorless and transparent, and the treated wastewater can be recycled as reclaimed water to realize the recycling of the water;
(3) the industrial byproduct chlorine water is effectively utilized, the resource utilization of the industrial byproduct chlorine water is realized, the discharge of waste liquid is reduced, the dosage of electron beam irradiation is also reduced, and the aims of energy conservation, emission reduction and environmental friendliness are achieved.
Detailed Description
It is easily understood that according to the technical solution of the present invention, a person skilled in the art can propose various alternative structures and implementation ways without changing the spirit of the present invention. Therefore, the following detailed description is merely illustrative of the technical solutions of the present invention, and should not be construed as being all of the present invention or limiting or restricting the technical solutions of the present invention.
A method for deeply treating organic wastewater by using micro-channels in cooperation with chlorine water and electron beams comprises the following steps:
s1, introducing chlorine water and organic wastewater into the microchannel reactor to obtain intermediate liquid;
s2, irradiating the interstitial fluid by using an electron beam, and adding a flocculating agent into the effluent for precipitation;
s3, filtering the mixed solution obtained in the S2, adding a reducing agent, and obtaining reclaimed water with COD less than 50ppm and SS less than 10mg/L through an RO membrane.
The organic wastewater to be treated in the invention is the organic wastewater pretreated by a biochemical pool, COD is less than 1000ppm, SS is less than 100mg/L, turbidity is less than 300NTU, pH value is 6-8, the characteristic pollutants are mainly heterocyclic organic matters such as pyridine rings and derivatives thereof, the color is reddish brown, chlorine water is a byproduct in the production process of chlor-alkali, and the content of free chlorine and available chlorine is 3000-10000 ppm.
In the S1 process, the byproduct chlorine water in the direct chlor-alkali production process reacts with the pretreated organic wastewater, so that the industrial byproduct chlorine water is effectively utilized, the resource utilization of the industrial byproduct chlorine water is realized, the discharge of waste liquid is reduced, the dosage of electron beam irradiation is also reduced, and the aims of energy conservation, emission reduction and environmental friendliness are achieved.
The whole process is finished in a micro-channel reactor, and the mass ratio of chlorine water to organic wastewater is 1-30: 100, preferably 10 to 15: 100, respectively; the reaction temperature is 30-150 ℃, preferably 90-120 ℃; the reaction residence time is 10 to 120s, preferably 30 to 60 s; due to the synergistic effect of the microchannel reactor, the contact probability of effective chlorine and free chlorine with organic matters in the wastewater is increased, the heat and mass transfer is enhanced, and the reaction efficiency and the oxidation efficiency are improved.
In S2, electron beam irradiation is used to excite water molecules to generate OH and H through the direct radiation of high-energy electron beam2O2And (2) the organic matters in the wastewater are further oxidized by equal-strength oxidation particles, so that the main chain of the organic macromolecular chain is broken and decomposed, the irradiation dose of the electron beam is 1kGy-15kGy, preferably 5kGy-10kGy, and the electron beam irradiation technology is used for replacing an oxidant, so that the high efficiency and automation of wastewater treatment are realized, and the safety, environmental protection and cleanness of the wastewater treatment are realized. Adding a flocculating agent into the effluent, wherein the flocculating agent can be PSAA, PFSS, PAC, PSF, preferably PAC; the mass ratio of the flocculating agent to the effluent is (0.005-0.05): 100, preferably (0.008 to 0.02): 100.
in S3, the reducing agent can be sodium sulfite or sodium bisulfite, preferably sodium sulfite, and the amount of the reducing agent is 10-1000mg/L, preferably 300-600 mg/L, and the reaction time is 0.5-3h, preferably 1-2 h.
The following embodiments are specifically described below.
Example 1
Respectively pumping the pretreated organic wastewater and chlorine water into a first module of a microchannel reactor for reaction, wherein the COD is 664ppm, the SS is 97mg/L, the turbidity is 251NTU, the mass ratio of the chlorine water to the organic wastewater is (1: 10) (the effective chlorine is 4500ppm), the reaction temperature is 100 ℃, the retention time is 60s, after the reaction is finished, carrying out electron beam irradiation on the organic wastewater, the irradiation amount is 10kGy, after the irradiation is finished, adding PAC into the reaction liquid, the mass ratio of the PAC to the reaction liquid is (0.01:100), after flocculation precipitation, filtering, the effective chlorine is 73ppm, the COD is 58ppm, adding sodium sulfite, the use amount is 332mg/L, carrying out mixed reaction for 1h, passing through a 0.45 micron precision filter, measuring that the COD is 52ppm, the effective chlorine is not detected, the SS is 12mg/L, the turbidity is 0.3NTU, passing through a membrane, the COD is 35ppm, the SS is 7mg/L, and the turbidity is 0.2U, meets the recycling requirement.
Example 2
Respectively pumping the pretreated organic wastewater and chlorine water into a first module of a microchannel reactor for reaction, the COD is 795ppm, the SS is 94mg/L, the turbidity is 269NTU, the mass ratio of the chlorine water to the organic wastewater is (1.2: 10) (the available chlorine is 4200ppm), the reaction temperature is 100 ℃, the retention time is 60s, after the reaction is finished, performing electron beam irradiation on the solution with irradiation dose of 8kGy, adding PAC (polyaluminium chloride) into the reaction solution after the irradiation is finished, wherein the mass ratio of the PAC to the reaction solution is (0.01:100), performing flocculation precipitation, filtering, adding sodium sulfite, wherein the effective chlorine is 82ppm, the COD is 68ppm, the dosage of which is 350mg/L, the mixture is mixed and reacted for 1 hour, and the mixture passes through a 0.45 micron precision filter, the COD is 62ppm, no effective chlorine is detected, SS is 9mg/L, the turbidity is 0.3NTU, the COD is 42ppm, SS is 5mg/L and the turbidity is 0.2NTU after passing through an RO membrane, and the recycling requirement is met.
Example 3
Respectively pumping the pretreated organic wastewater and chlorine water into a first module of a microchannel reactor for reaction, the COD is 998ppm, the SS is 98mg/L, the mass ratio of the chlorine water to the organic wastewater is (1.5: 10) (the available chlorine is 4800ppm), the reaction temperature is 100 ℃, the retention time is 60s, after the reaction is finished, performing electron beam irradiation with irradiation dose of 5kGy, adding PAC (polyaluminium chloride) into the reaction solution after the irradiation is finished, wherein the mass ratio of the PAC to the reaction solution is (0.01:100), performing flocculation precipitation, filtering to obtain 95ppm of available chlorine and 75ppm of COD, adding sodium sulfite, the dosage of which is 380mg/L, mixing and reacting for 1h, passing through a 0.45 micron precision filter, the COD is 69ppm, no effective chlorine is detected, SS is 10mg/L, the turbidity is 0.3NTU, and the COD is 48ppm, SS is 2mg/L and the turbidity is 0.2NTU after passing through an RO membrane, thereby meeting the recycling requirement.
It can be seen from the above examples that the use of electron beams instead of oxidants realizes the safety and cleanness of the oxidation process while efficiently reducing COD, and the addition of chlorine water also reduces the dosage of electron irradiation dose.
The technical scope of the present invention is not limited to the above description, and those skilled in the art can make various changes and modifications to the above-described embodiments without departing from the technical spirit of the present invention, and such changes and modifications should fall within the protective scope of the present invention.
Claims (8)
1. A method for deeply treating organic wastewater by using micro-channels in cooperation with chlorine water and electron beams is characterized by comprising the following steps:
s1, introducing chlorine water and organic wastewater into the microchannel reactor to obtain intermediate liquid;
s2, irradiating the interstitial fluid by using an electron beam, and adding a flocculating agent into the effluent for precipitation;
s3, filtering the mixed solution obtained in the S2, adding a reducing agent, and obtaining reclaimed water with COD less than 50ppm and SS less than 10mg/L through an RO membrane;
the mass ratio of the chlorine water to the organic wastewater in S1 is 1-30: 100.
2. the method for advanced treatment of organic wastewater by using the micro-channel in cooperation with chlorine water and the electron beam as claimed in claim 1, wherein the irradiation dose of the electron beam is 1-15kGy, and the electron beam irradiation excites the intermediate solution to generate strong oxidation particles to complete the oxidation reaction.
3. The method for advanced treatment of organic wastewater by using micro-channels in cooperation with chlorine water and electron beams as claimed in claim 1, wherein the flocculating agent is any one of PSAA, PFSS, PAC and PSF, and the mass ratio of the flocculating agent to effluent is 0.005-0.05: 100.
4. The method for advanced treatment of organic wastewater by using micro-channels in cooperation with chlorine water and electron beams as claimed in claim 1, wherein the reducing agent is any one of sodium sulfite and sodium bisulfite.
5. The method for advanced treatment of organic wastewater by using micro-channels in cooperation with chlorine water and electron beams as claimed in claim 1, wherein the amount of the reducing agent is 10-1000mg/L, and the reaction time in S3 is 0.5-3 h.
6. The method for advanced treatment of organic wastewater by using micro-channels in cooperation with chlorine water and electron beams as claimed in claim 1, wherein the reaction temperature in the S1 is 30-150 ℃ and the reaction residence time is 10-120S.
7. The method of claim 1, wherein the organic wastewater has COD < 1000ppm, SS < 100mg/L, turbidity < 300NTU, pH 6-8, reddish brown color, and characteristic contaminants mainly including heterocyclic organic compounds such as pyridine ring and derivatives thereof.
8. The method as claimed in claim 7, wherein the chlorine water is a byproduct in the chlor-alkali production process, and the total content of free chlorine and available chlorine is 3000-10000 ppm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106219816A (en) * | 2016-08-25 | 2016-12-14 | 万华化学集团股份有限公司 | A kind of processing method of reverse osmosis concentrated water |
| US20170107137A1 (en) * | 2014-09-24 | 2017-04-20 | Techwin Co, Ltd. | Resource reuse-type industrial waste water treatment method and apparatus utilizing oxidizing agent generated by utilizing waste water |
| CN108773894A (en) * | 2018-06-07 | 2018-11-09 | 山东理工大学 | A kind of method and its device using micro passage reaction treating technology continuous processing high COD organic wastewater with high salt |
| CN113024000A (en) * | 2021-03-10 | 2021-06-25 | 清华大学 | Method for pretreating or deeply treating industrial wastewater by adopting electron beam irradiation coupling Fenton technology |
| CN213680292U (en) * | 2020-11-13 | 2021-07-13 | 四川全息生态环境技术产业有限公司 | Electron beam micro chemical oxidation device |
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- 2021-09-13 CN CN202111077220.0A patent/CN113830941A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170107137A1 (en) * | 2014-09-24 | 2017-04-20 | Techwin Co, Ltd. | Resource reuse-type industrial waste water treatment method and apparatus utilizing oxidizing agent generated by utilizing waste water |
| CN106219816A (en) * | 2016-08-25 | 2016-12-14 | 万华化学集团股份有限公司 | A kind of processing method of reverse osmosis concentrated water |
| CN108773894A (en) * | 2018-06-07 | 2018-11-09 | 山东理工大学 | A kind of method and its device using micro passage reaction treating technology continuous processing high COD organic wastewater with high salt |
| CN213680292U (en) * | 2020-11-13 | 2021-07-13 | 四川全息生态环境技术产业有限公司 | Electron beam micro chemical oxidation device |
| CN113024000A (en) * | 2021-03-10 | 2021-06-25 | 清华大学 | Method for pretreating or deeply treating industrial wastewater by adopting electron beam irradiation coupling Fenton technology |
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