CN113526778A - Treatment process of high-concentration industrial wastewater - Google Patents
Treatment process of high-concentration industrial wastewater Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
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- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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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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- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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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- C02F2001/007—Processes including a sedimentation step
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
- C02F3/30—Aerobic and anaerobic processes
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Abstract
The invention provides a treatment process of high-concentration industrial wastewater, which comprises the following steps of sequentially treating the chemical wastewater: (1) classified collection, oil separation and sedimentation; (2) micro-electrolysis decomposition; (3) neutralizing and coagulating by Fenton oxidation (4); (5) flocculation; (6) precipitation and sludge backflow; (7) then neutralizing; (8) and (4) performing biochemical treatment. The acid-base wastewater is separately treated, so that the generation of difficultly degraded precipitates or complexes when the two types of wastewater are mixed can be avoided; before entering a micro-electrolysis reaction tank, the alkaline wastewater is properly used as a pH regulator, so that the adding amount of the pH regulator in the whole system is reduced; in the process, part of the precipitated sludge flows back to the pH neutralization tank, so that the fluorine removal effect is improved; the domestic wastewater is mixed with the production wastewater after the physicochemical treatment, so that organic nutrient substances which are easy to be biochemical can be introduced, the salt concentration in the water is further reduced, and the protection effect on microorganisms is achieved; the process solves the problems of high investment and high operation cost in chemical wastewater treatment.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a treatment process of high-concentration industrial wastewater.
Background
The fluorine chemical wastewater has high salinity and high organic matter concentration and is difficult to carry out biochemical treatment. And has certain carcinogenic effect on tissue systems of human bodies. The main pollutants are F-containing compounds, refractory organic matters and the like. The traditional chemical wastewater treatment processes such as a chemical precipitation method, an electrolysis method, a biological method and the like have the limitations of poor effect, secondary pollution and the like.
The disclosed method for treating fluorine-containing waste water includes "a fluorine-containing waste water treatment apparatus based on Fenton oxidation" (application No. 201220640800.6), which is invented by Xunjian, etc. of Suzhou city environmental protection Co., Ltd. The device comprises (in pipeline connection order): the device comprises a regulating tank, an oxidation tank, a coagulation tank, a dosing reaction tank, a flocculation tank, a sedimentation tank and a sludge concentration tank, wherein the sludge concentration tank is connected with a plate-and-frame filter press. Although the process flow of the method is simple and is easy to realize the automatic operation of wastewater treatment facilities, the process only adopts physicochemical treatment and cannot ensure the purification rate of the wastewater; in addition, the fluorine chemical wastewater comprises acid wastewater and alkaline wastewater, and the process can intensively treat the wastewater with two properties to generate precipitate or complex, so that the problems of unstable water quality parameters, high treatment difficulty, high treatment cost and the like are easily caused, and finally the effluent quality does not reach the standard.
Disclosure of Invention
The invention provides a novel process for treating high-concentration fluorine chemical wastewater, which aims to solve the problems of high toxicity and difficult biodegradation of the high-concentration fluorine chemical wastewater, the problem of utilization of waste acid in a factory, the problems of high investment and poor treatment effect of the chemical wastewater treatment and the like, and comprises the following steps: (1) dividing chemical wastewater into acidic wastewater and alkaline wastewater, respectively carrying out oil separation and sedimentation treatment on the wastewater with two properties, respectively sending the treated wastewater into an acidic storage tank and an alkaline storage tank, and mixing the wastewater in the alkaline storage tank with the wastewater in the acidic storage tank after removing ammonia nitrogen by air stripping; (2) adjusting the pH value of the mixed effluent to 2-4 by using a pH regulator, and then feeding the mixed effluent into a micro-electrolysis reaction tank for micro-electrolysis decomposition; (3) the effluent after micro-electrolysis enters an oxidation reaction tank for Fenton oxidation reaction; (4) the effluent of the Fenton oxidation reaction enters a neutralization tank, a regulator is added to adjust the pH value of the wastewater in the neutralization tank to 8, and coagulation reaction is carried out, wherein the regulator comprises Ca (OH) 2; (5) the effluent of the coagulation reaction enters a flocculation tank, and a flocculating agent is added for flocculation reaction; (6) the effluent of the flocculation reaction enters a precipitation tank, and solid-liquid separation is carried out in the precipitation tank to obtain supernatant and sludge; (7) the supernatant enters a re-neutralization tank, and H2SO4 and nutritive salt are added for regulation SO that the supernatant is suitable for the growth of microorganisms; (8) and performing biochemical treatment on the effluent after being regulated by the secondary neutralization tank.
And (3) using an iron-carbon filler during the micro-electrolysis decomposition in the step (2), wherein the iron-carbon filler is an ideal filler for micro-electrolysis at present.
The regulator in the step (2) can be sulfuric acid or sodium hydroxide.
The Fe2+ formed by electrolysis in the micro-electrolysis reaction process in the step (2) enters an oxidation reaction tank as a step
(3) A catalyst for the fenton oxidation reaction.
The regulator in the step (4) also comprises waste water in the alkaline storage tank after ammonia nitrogen is removed through air stripping, and the waste water in the alkaline storage tank is properly used as a pH regulator, so that the dosage of alkaline agents in the whole system can be reduced, and the cost is saved.
The flocculant of step (5) may be PAM.
Discharging sludge obtained by solid-liquid separation in the precipitation tank into a sludge concentration tank; in a further preferred embodiment, a part of the sludge is returned to the pH neutralization tank, the other part of the sludge is discharged to the sludge concentration tank, and a part of the precipitated sludge is returned to the pH neutralization tank, so that the sludge containing CaF2 precipitate is used as a precipitation seed crystal to enhance the defluorination effect. The biochemical treatment process in the step (8) comprises the steps of uniformly mixing at least one of domestic sewage and initial rainwater in the production area and the effluent water regulated by the secondary neutralization tank in the step (7) in the comprehensive regulation tank, controlling the salinity of the influent water to be 1-2 percent (mass fraction), and adjusting the temperature in the comprehensive regulation tank to be 35 ℃, so that the production wastewater can be diluted, the concentration of the production wastewater is reduced, the salinity is reduced, and the salinity of the influent water is ensured to be 1-2 percent (mass fraction); the effluent adjusted by the comprehensive adjusting tank enters an anaerobic stage and an aerobic stage for treatment.
The anaerobic stage is divided into an anaerobic stage and a facultative anaerobic stage; the aerobic stage is divided into a first-stage contact oxidation stage and a second-stage contact oxidation stage; and the reflux ratio of each stage of the process was 200%. On one hand, the reflux can play a role in dilution, and on the other hand, the amount of microorganisms in the primary and secondary contact oxidation ponds can be supplemented; if the reflux ratio is too low to achieve the treatment effect, and too high, the treatment cost is increased.
The first-stage contact oxidation stage comprises the step of enabling effluent treated in the anaerobic stage to sequentially enter a first-stage contact oxidation tank and a middle sedimentation tank; the secondary contact oxidation stage comprises that the effluent treated by the intermediate sedimentation tank sequentially enters a secondary contact oxidation tank and a secondary sedimentation tank; and filling materials for the growth of halotolerant bacteria, preferably combined filling materials, are added into the primary contact oxidation tank and the secondary contact oxidation tank.
Preferably, the sludge obtained by the secondary sedimentation tank treatment is discharged into the sludge concentration tank through the sludge storage tank.
Supernatant obtained by the treatment of the sludge concentration tank flows into the comprehensive adjusting tank.
Preferably, the sludge at the bottom of the sludge concentration tank is conveyed into a filter press by a sludge pressure pump for filter pressing, filter residues generated by the filter pressing are conveyed to a professional solid waste treatment mechanism for treatment, and filter liquor of the filter press returns to the comprehensive adjusting tank.
Compared with the prior art, the invention has the following advantages:
1. the fluorine chemical wastewater is divided into 2 types, namely firstly, the wastewater containing acidic wastewater and secondly, the wastewater containing alkaline wastewater are subjected to oil separation and sedimentation treatment respectively, the treated wastewater is respectively sent into an acidic storage tank and an alkaline storage tank, and the wastewater in the alkaline storage tank is mixed with the wastewater in the acidic storage tank after ammonia nitrogen is removed by air stripping, so that the problems of precipitation and complex generated by directly mixing two water qualities and unstable water quality parameters are avoided, and the treatment cost is reduced; before entering the micro-electrolysis reaction tank, the wastewater in the alkaline storage tank after ammonia nitrogen is removed by air stripping is mixed with the wastewater in the acidic storage tank, so that the pH of the wastewater is properly adjusted by utilizing the neutralization effect of the acidic and alkaline wastewater, the shortage of part of the wastewater is adjusted by using a pH regulator, the adding amount of the pH regulator in the whole system is reduced, and the operation cost is reduced.
2. Fe2+ formed by electrolysis in a micro-electrolysis cell is utilized in Fenton oxidation reaction, so that the cost for purchasing Fe2+ medicament is reduced, and the operation cost is reduced.
3. In the neutralization tank, the waste water in the alkaline storage tank after ammonia nitrogen is removed by air stripping is properly used as a pH regulator, so that the dosage of alkaline agents in the whole system is reduced, and the operation cost is reduced.
4. Part of the precipitated sludge is returned to the pH neutralization tank, and the original CaF2 precipitated sludge is used as a precipitation seed crystal to enhance the defluorination effect.
5. The domestic sewage and initial rainwater in the production area are mixed with the high-concentration production wastewater after physicochemical treatment, other wastewater in a plant area is effectively utilized, on one hand, organic nutrient substances which are easy to be biochemically generated can be introduced, on the other hand, the salinity of the water is further reduced and controlled to be 1-2%, the microorganism is protected, and the method is beneficial to the next biochemical reaction.
6. The anaerobic stage in the biochemical treatment process is divided into an anaerobic stage and a facultative anaerobic stage; the aerobic stage is divided into a first-stage contact oxidation stage and a second-stage contact oxidation stage; and the reflux ratio of each stage of the process was 200%. On one hand, the reflux can play a role in dilution, and on the other hand, the amount of microorganisms can be supplemented; if the reflux ratio is too low to achieve the treatment effect, and too high, the treatment cost is increased. Meanwhile, the oxidation stage adopts combined fillers, which is suitable for the growth of halotolerant bacteria.
7. The chemical wastewater treatment process has the characteristics of low treatment cost, high purification efficiency and the like.
Detailed Description
The invention is further illustrated by the following examples:
example 1: 300 tons of wastewater produced by a certain factory in the Fuxin fluorine chemical industry park are treated by the following process:
the chemical wastewater is classified into 2 types by the chemical wastewater classification collection, oil separation and sedimentation units, namely firstly, acidic wastewater and secondly, alkaline wastewater. Chemical wastewater produced in chemical production line
And (3) discharging the wastewater into corresponding wastewater oil separation settling tanks through pipelines in a classified manner for oil separation treatment and settling treatment, respectively sending the treated wastewater into an acidic storage tank and an alkaline storage tank, wherein the HRT of the wastewater in the storage tanks is =10h, and mixing the wastewater in the alkaline storage tanks with the wastewater in the acidic storage tanks after ammonia nitrogen is removed by air stripping.
The pH value of the mixed effluent is adjusted to 2-4 by the acid wastewater micro-electrolysis unit by using a pH regulator, and then the effluent enters a micro-electrolysis reaction tank for micro-electrolysis decomposition.
The microelectrolysis reaction formula is as follows:
anode (Fe): Fe-2 e → Fe2+,
a cathode (C) of 2H + +2e → 2[ H ] → H2,
in the reaction, nascent Fe2+ and atomic H are generated, which have high chemical activity and can change the structure and characteristics of a plurality of organic matters in the wastewater, cause chain scission and ring opening of the organic matters, remove chromaticity in the water, improve the biodegradability of the wastewater and the like.
The micro-electrolysis decomposition is carried out under the aeration state, because the aeration can play a role of stirring, the hardening of scrap iron is relieved, and the service life of the micro-electrolysis bath is prolonged. HRT =2d of wastewater in the micro-electrolysis cell.
Effluent of the acidic wastewater Fenton oxidation unit after micro-electrolysis decomposition enters an oxidation reaction tank for Fenton oxidation reaction, and the Fenton reaction is a series of free radical reactions taking ferrous ions as catalysts.
The fenton reagent continuously generates HO (hydroxyl radical, electrode potential 2.80EV, second only to F2) through the reaction, so that the whole system has strong oxidizing property and can oxidize chlorobenzene, benzyl chloride, grease and other substances which are difficult to be oxidized by common oxidizing agents. The biochemical property of the wastewater is further improved, and the HRT =48min of the wastewater in the oxidation reaction tank.
The effluent of Fenton reaction in the adjusting and coagulating unit enters a neutralizing tank, Ca (OH)2 is added to adjust the pH value to about 8, on one hand, the pH value in the water is adjusted by utilizing the alkalinity of the Ca (OH)2, and Fe3+ is formed into Fe (OH) 3 colloidal flocculant, so that pollutants in the water can be effectively adsorbed and coagulated, and the wastewater purifying effect is enhanced. On the other hand, Ca 2+ in Ca (OH)2 is utilized to form CaF2 precipitate with F-in the wastewater, and F-in the water is removed. In the process, alkaline waste water is properly added for adjusting the pH value, thereby saving a large amount of medicaments. HRT =24min in the neutralization tank.
Flocculation unit
And (3) enabling effluent of the coagulation reaction to enter a flocculation tank, and adding a proper amount of PAM (polyacrylamide) for flocculation reaction, so that flocs formed by coagulation are larger.
The effluent of the flocculation reaction of the sedimentation and sludge backflow unit flows into a sedimentation tank. Solid-liquid separation is carried out in the precipitation tank, partial precipitation sludge flows back to the pH neutralization tank, and the sludge containing CaF2 precipitation is used as precipitation seed crystals to enhance the fluorine removal effect. And the supernatant obtained by the solid-liquid separation of the re-neutralization unit in the precipitation tank enters the re-neutralization tank, and H2SO4 and nutritive salt are added to adjust the water quality SO that the water quality is suitable for the growth of microorganisms. Integrated waste water treatment unit the integrated waste water treatment unit may also be understood as a biochemical treatment stage. According to the characteristics of the sewage quality of some fluoridation factories, the waste water of the fluoridation factory has the characteristics of toxicity, irritation, unstable pH, high COD and the like, and the comprehensive waste water treatment unit can effectively remove the COD in the waste water, so that the comprehensive waste water treatment unit is necessary for the waste water of the fluoridation factory, the effluent water regulated by the secondary neutralization tank and the production and domestic sewage are uniformly mixed in the comprehensive regulation tank, the concentration of the waste water is diluted, and the salinity is controlled to be 1-2%. The comprehensive treatment unit effectively utilizes other waste water in a plant area, can dilute the production waste water, introduces organic nutrient substances which are easy to be biochemical and provides possibility for biochemical reaction. The temperature of the wastewater in the comprehensive adjusting tank is adjusted to 35 ℃. The effluent of the anaerobic and aerobic treatment units, which is regulated by the comprehensive regulation tank, enters an anaerobic stage and an aerobic stage for treatment. The anaerobic stage is divided into an anaerobic stage and a facultative anaerobic stage, the aerobic stage is divided into a first-stage contact oxidation stage and a second-stage contact oxidation stage, the reflux ratio of each stage of process is 200%, HRT =24h, and the first-stage contact oxidation stage comprises that effluent treated in the anaerobic stage sequentially enters a first-stage contact oxidation tank and a middle sedimentation tank; the secondary contact oxidation stage comprises that effluent treated in the primary contact oxidation stage sequentially enters a secondary contact oxidation tank and a secondary sedimentation tank; meanwhile, the combined filler is added into the first-stage contact oxidation tank and the second-stage contact oxidation tank to ensure the growth of the halotolerant bacteria. The treated water quality is superior to the national comprehensive wastewater discharge standard, the effluent is clear, the operation stability and the operation cost are lower than those of the similar wastewater treatment process, and the effluent quality is shown in Table 2.
The sludge treatment unit is used for carrying out subsequent treatment on the generated sludge, and part of the sludge accumulated at the bottom of the settling tank is periodically discharged into a sludge concentration tank; sludge obtained by the secondary sedimentation tank treatment is discharged into a sludge concentration tank periodically after passing through a sludge storage tank; the sludge concentration tank plays a role in further reducing the water content of the sludge, the obtained supernatant flows into the comprehensive adjusting tank, and the sludge at the bottom of the sludge concentration tank is conveyed to the membrane filter press by the sludge pressure pump at regular intervals for filter pressing. And (4) periodically transporting dry sludge generated by filter pressing to a professional solid waste treatment mechanism for treatment. The filtrate of the filter press returns to the comprehensive adjusting tank.
Claims (10)
1. A treatment process of high-concentration industrial wastewater is characterized by comprising the following steps: (1) dividing chemical wastewater into acidic wastewater and alkaline wastewater, respectively carrying out oil separation and sedimentation treatment on the wastewater with two properties, respectively sending the treated wastewater into an acidic storage tank and an alkaline storage tank, and mixing the wastewater in the alkaline storage tank with the wastewater in the acidic storage tank after removing ammonia nitrogen by air stripping; (2) adjusting the pH value of the mixed effluent to 2-4 by using a pH regulator, and then feeding the mixed effluent into a micro-electrolysis reaction tank for micro-electrolysis decomposition; (3) the effluent after micro-electrolysis enters an oxidation reaction tank for Fenton oxidation reaction; (4) the effluent of the Fenton oxidation reaction enters a neutralization tank, a regulator is added to adjust the pH value in the neutralization tank to 8, and coagulation reaction is carried out, wherein the regulator comprises Ca (OH) 2; (5) the effluent of the coagulation reaction enters a flocculation tank, and a flocculating agent is added for flocculation reaction; (6) the effluent of the flocculation reaction enters a precipitation tank, and solid-liquid separation is carried out in the precipitation tank to obtain supernatant and sludge; (7) the supernatant enters a re-neutralization tank, and H2SO4 and nutrient salt are added for regulation; (8) and performing biochemical treatment on the effluent after being regulated by the secondary neutralization tank.
2. The process for treating high-concentration industrial wastewater according to claim 1, wherein: and (3) feeding Fe2+ electrolytically formed in the micro-electrolytic decomposition process in the step (2) into an oxidation reaction tank to be used as a catalyst for the Fenton oxidation reaction in the step (3).
3. The process for treating high-concentration industrial wastewater according to claim 1, wherein: the regulator in the step (4) also comprises the waste water in the alkaline storage tank after ammonia nitrogen is removed through air stripping.
4. The process for treating high-concentration industrial wastewater according to claim 1, wherein: and (6) discharging sludge obtained by solid-liquid separation in the precipitation tank into a sludge concentration tank, or returning a part of sludge to the pH neutralization tank, and discharging the other part of sludge into the sludge concentration tank.
5. The process for treating high-concentration industrial wastewater according to claim 1, wherein: and (8) the biochemical treatment process comprises uniformly mixing at least one of domestic sewage and initial rainwater in the production area and the effluent regulated by the re-neutralizing tank in the step (7) in the comprehensive regulating tank, controlling the salinity of the influent water to be 1-2%, regulating the temperature in the comprehensive regulating tank to be 35 ℃, and then treating the effluent regulated by the comprehensive regulating tank in an anaerobic stage and an aerobic stage.
6. The process for treating high-concentration industrial wastewater according to claim 5, wherein: the anaerobic stage is divided into an anaerobic stage and a facultative anaerobic stage; the aerobic stage is divided into a first-stage contact oxidation stage and a second-stage contact oxidation stage; and the reflux ratio of each stage was 200%.
7. The process for treating high-concentration industrial wastewater according to claim 6, wherein: the first-stage contact oxidation stage comprises the step of enabling effluent treated in the anaerobic stage to sequentially enter a first-stage contact oxidation tank and a middle sedimentation tank; the secondary contact oxidation stage comprises that the effluent treated by the intermediate sedimentation tank sequentially enters a secondary contact oxidation tank and a secondary sedimentation tank; and filling materials for the growth of halotolerant bacteria are added into the primary contact oxidation pond and the secondary contact oxidation pond.
8. The process for treating high-concentration industrial wastewater according to claim 7, wherein: and discharging the sludge obtained by the secondary sedimentation tank treatment into a sludge concentration tank through a sludge storage tank.
9. The process for treating high concentration industrial wastewater according to claim 4 or 8, wherein: supernatant obtained by the treatment of the sludge concentration tank flows into the comprehensive adjusting tank.
10. The process for treating high concentration industrial wastewater according to claim 4 or 8, wherein: sludge at the bottom of the sludge concentration tank is conveyed to a filter press by a sludge pressure pump for filter pressing, filter residues generated by filter pressing are conveyed to a professional solid waste treatment mechanism for treatment, and filter liquor of the filter press returns to the comprehensive adjusting tank.
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| JP7403781B1 (en) | 2023-05-16 | 2023-12-25 | オリエンタル白石株式会社 | Methane fermentation equipment and methane fermentation method |
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| JP7403781B1 (en) | 2023-05-16 | 2023-12-25 | オリエンタル白石株式会社 | Methane fermentation equipment and methane fermentation method |
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