CN111573969A - Combined biological treatment method for high-concentration COD chromium-containing electroplating cleaning wastewater - Google Patents
Combined biological treatment method for high-concentration COD chromium-containing electroplating cleaning wastewater Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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Abstract
The invention relates to a combined biological treatment method of high-concentration COD chromium-containing electroplating cleaning wastewater, which is characterized in that the wastewater is treated by a regulating tank, a primary filtering unit, an oxidation unit, a biodegradation unit and a post-filtering unit in sequence and then is discharged up to the standard and directly recycled or recycled after being subjected to advanced treatment. The invention organically combines the heterogeneous catalytic oxidation technology and the biotechnology, supplements the two treatment technologies, and finishes the synergistic removal of heavy metals such as high-concentration COD, low ammonia nitrogen, total phosphorus, hexavalent chromium and the like and other various pollutants aiming at the high-concentration COD chromium-containing electroplating cleaning organic wastewater which is difficult to treat. The nondegradable wastewater is subjected to heterogeneous catalytic oxidation regulation to create an advantageous environment for subsequent biological treatment of specific strains, so that hexavalent chromium detoxification and organic pollutant removal are simultaneously completed. Chemical agents are not required to be added in the whole treatment process, the ion concentration in the wastewater is not increased, the wastewater is finally discharged up to the standard or reused as the supplementary water for enterprise production, and the wastewater is purified or recycled.
Description
Technical Field
The invention relates to the technical field of industrial wastewater purification treatment, in particular to a combined biological treatment method for high-concentration COD chromium-containing electroplating cleaning wastewater.
Background
The metal chromium has the advantages of high hardness, small friction coefficient, good chemical stability and the like, is widely applied as a protective and decorative coating and occupies a high proportion in the electroplating industry. The electroplating cleaning wastewater produced by enterprises is mainly mixed water of cleaning oil-removing wastewater, rinsing wastewater, passivation wastewater and the like in the pretreatment process of a piece to be plated, and the wastewater has the characteristics of containing a large amount of oil, high COD (chemical oxygen demand) concentration, low ammonia nitrogen concentration, strong alkaline pH value and more inorganic salt components including heavy metal ion chromium. The toxicity of chromium is related to the valence state of chromium, the toxicity of hexavalent chromium is obviously higher than that of trivalent chromium, and a part of chromium ions in electroplating cleaning wastewater generated by enterprises are hexavalent chromium due to the characteristics of pollutants, so that the chromium ions have high toxicity and poor biodegradability, and the chromium ions belong to industrial organic wastewater which is difficult to treat.
In recent years, research on a biotechnological treatment method of wastewater by utilizing microorganisms to enrich and metabolize heavy metals is gradually started, and the method is considered to be a pollution treatment method with great development potential due to the characteristics of economy, high efficiency, no secondary pollution and the like. However, the specific bacteria species usually have specific requirements for the wastewater with respect to the contaminant concentration, pH, dissolved oxygen, temperature, etc. due to the limitations of the organisms themselves. Because the electroplating cleaning wastewater has high toxicity, high COD concentration and high refractory components, the traditional biological treatment process can hardly be applied, and at least the reduction of the toxicity of the electroplating wastewater needs to be considered firstly, namely hexavalent chromium needs to be reduced into trivalent chromium firstly, and then precipitate is formed to realize pollutant separation. The treatment technologies include reduction treatment technologies such as a sulfite method, a ferrous sulfate-lime method, an electrolytic reduction method and the like, and physicochemical treatment technologies such as electrodialysis, reverse osmosis, ion exchange, activated carbon adsorption, flocculation and the like, which are common, the treatment technologies generally have the problems of large energy and medicament consumption, high investment and operation cost, and the generation of a large amount of chromium-containing waste which needs to be treated separately, and the chromium ion concentration of the electroplating cleaning wastewater is not in the applicable concentration range of the treatment technologies, so that the technical and economic indexes are poor.
Therefore, aiming at the high-concentration COD chromium-containing electroplating cleaning wastewater generated by electroplating enterprises, a method with high efficiency and low cost is still required to be searched for targeted purification treatment.
Disclosure of Invention
The invention provides a combined biological treatment method of high-concentration COD chromium-containing electroplating cleaning wastewater, which organically combines a heterogeneous catalytic oxidation technology and a biological technology; aiming at the high-concentration COD chromium-containing electroplating cleaning organic wastewater which is difficult to treat, the method completes the synergistic removal of heavy metals such as high-concentration COD, low ammonia nitrogen, total phosphorus, hexavalent chromium and the like and other various pollutants. The nondegradable wastewater is subjected to heterogeneous catalytic oxidation regulation to create an advantageous environment for subsequent biological treatment of specific strains, so that hexavalent chromium detoxification and organic pollutant removal are simultaneously completed. The whole treatment process does not need to add chemical agents outside, does not increase the ion concentration in the wastewater, finally realizes standard discharge or is recycled as the supplementary water for enterprise production, and realizes the purification or resource utilization of the wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a combined biological treatment method of high-concentration COD chromium-containing electroplating cleaning wastewater is disclosed, wherein the COD concentration in the electroplating cleaning wastewater is more than or equal to 2000mg/L, and the concentration of hexavalent chromium is less than or equal to 10 mg/L; the processing method comprises the following steps:
(1) firstly, feeding the wastewater into a regulating tank, and homogenizing;
(2) the effluent of the regulating reservoir is sent into a primary filtering unit to remove large-particle insoluble impurities in the wastewater;
(3) the effluent of the primary filtering unit is sent into an oxidizing unit; the oxidation unit adopts heterogeneous catalytic oxidation, carries out chain scission on complex organic pollutants in the wastewater under the action of a catalyst at normal temperature and normal pressure, improves the biodegradability of the wastewater, and simultaneously adjusts the property of the wastewater to ensure that the wastewater meets the requirements of the subsequent process;
(4) the effluent of the oxidation unit is sent to a biodegradation unit; the large carbon chain organic matter obtained by the preliminary degradation of the wastewater through the oxidation unit is further degraded into small carbon chain and single carbon chain organic matter, and finally converted into water, carbon dioxide and other small molecular inorganic matters; the biochemical reactions of oxidation and reduction in the biodegradation unit are alternately and repeatedly carried out, hexavalent chromium contained in the wastewater is reduced into precipitate of trivalent chromium, the precipitate is deposited at the bottom of the biodegradation unit, and the precipitate is periodically discharged;
(5) and (3) sending the effluent of the biodegradation unit into a post-filtering unit, removing redundant impurities in the wastewater, and then discharging the wastewater after reaching the standard and directly recycling the wastewater or recycling the wastewater after advanced treatment.
The filter medium in the primary filter unit is one or a combination of a plurality of porous filter media, granular filter media and alloy screens; wherein the porous filter medium is ceramic or nylon, and the filter aperture is 30-50 μm; the granular filter medium is one or two of manganese sand or quartz sand.
In the heterogeneous catalytic oxidation process in the oxidation unit, the catalyst adopts one or more of platinum, lead, nickel and copper oxides, and is sintered into a net-shaped or granular structure at high temperature; the oxidant is air or ozone.
The biodegradation unit is a full-flow anaerobic biodegradation process and comprises 2 process sections of a hydrolytic acidification section and an anaerobic digestion section; in the hydrolysis acidification section, large carbon chain organic matters contained in the wastewater are converted into small carbon chain hydrocarbon compounds, and a plurality of organic acids are contained in the products; in an acidic environment, hexavalent chromium in the wastewater is used as an electron acceptor, and the biological strain takes small carbon chain molecules as an electron donor to reduce the hexavalent chromium into trivalent chromium; in the anaerobic biological section, low-valence chromium ions generated by the reaction of the hydrolytic acidification section are combined with OH < - > in the wastewater in a weak alkali environment by means of metabolism of anaerobic biological strains to form low-valence chromium precipitates which are gradually separated from the wastewater; meanwhile, the small carbon chain organic pollutants are metabolized by the biological strains and finally converted into water, carbon dioxide and other inorganic substances; meanwhile, ammonia nitrogen and total phosphorus are also removed.
And the low-valence chromium precipitate is separately collected and used as a metal chromium smelting raw material.
The filtering medium in the post-filtering unit is one or more of quartz sand, anthracite, activated carbon, magnetite, manganese sand, ceramsite and porous ceramic, and the particle size of the filtering medium is 0.5-5 mm.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention adopts a combined biotechnology treatment method to specifically treat high-concentration COD chromium-containing electroplating cleaning wastewater with specific pollutant characteristics, can overcome the problem of poor tolerance of conventional biochemical treatment anaerobic strains to hexavalent chromium toxicity, and can simultaneously solve the defects of low treatment efficiency, single function and incapability of removing organic pollutants simultaneously of the existing anaerobic treatment chromium-containing wastewater to low-concentration hexavalent chromium. The process flow is optimized and combined, the non-degradable organic matters are subjected to chain scission through the chemical oxidation section, the biodegradability of the wastewater is improved, the property of the wastewater is adjusted, and an advantageous environmental condition is created for the growth of a specific strain in subsequent biological treatment, so that the detoxification and the removal of organic pollutants of hexavalent chromium can be simultaneously completed through the synergistic effect of the hydrolytic acidification of the biological degradation unit and the anaerobic process section. The two processes are organically combined, so that the waste water which is originally high in toxicity, high in concentration of pollutants difficult to degrade and poor in biodegradability can be efficiently and stably purified.
2) In the whole process of the wastewater treatment process, acid, alkali or other chemical agents are not required to be added externally, and the ion concentration in the wastewater treatment process is not increased, so that the conductivity before and after wastewater treatment cannot be increased, and the treated effluent can meet the cleaning and recycling water standard in the electroplating production link.
3) Solid waste is not discharged in a heterogeneous catalytic oxidation process link, and only a small amount of biological sludge metabolized by biological strains and low-valence chromium metal precipitates are generated in a biological strain biochemical reaction process of a biodegradation unit; the low-valence metal chromium precipitate and the biological sludge are discharged together as waste in the wastewater treatment process. The waste contains biological sludge and metal chromium, so that the waste can be used as a raw material for resource recycling, and zero emission of pollutants is realized.
4) In the biological treatment process of the high-concentration COD chromium-containing electroplating cleaning wastewater, each section of biological strain biochemical reaction is completed under the anoxic condition, so that hexavalent chromium contained in the wastewater is reduced into trivalent chromium and cannot be oxidized into hexavalent chromium again, thereby thoroughly eliminating the hexavalent chromium in the wastewater and ensuring the stable and reliable treatment effect.
5) Compared with the conventional technology for eliminating hexavalent chromium ions in wastewater by a chemical method, the method has the advantages of no toxicity, no harm and no waste; compared with the conventional biological activated sludge technology, the method has the advantages of less biological sludge production and less discharge.
6) The method has the advantages of good process stability, strong impact resistance, simple flow, simple operation, high efficiency, low cost and no secondary pollution, and is suitable for popularization and application.
Drawings
FIG. 1 is a process flow chart of the combined biological treatment method of high-concentration COD chromium-containing electroplating cleaning wastewater.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
as shown in figure 1, the combined biological treatment method of the high-concentration COD chromium-containing electroplating cleaning wastewater provided by the invention has the advantages that the COD concentration in the electroplating cleaning wastewater is more than or equal to 2000mg/L, and the hexavalent chromium concentration is less than or equal to 10 mg/L; the processing method comprises the following steps:
(1) firstly, feeding the wastewater into a regulating tank, and homogenizing;
(2) the effluent of the regulating reservoir is sent into a primary filtering unit to remove large-particle insoluble impurities in the wastewater;
(3) the effluent of the primary filtering unit is sent into an oxidizing unit; the oxidation unit adopts heterogeneous catalytic oxidation, carries out chain scission on complex organic pollutants in the wastewater under the action of a catalyst at normal temperature and normal pressure, improves the biodegradability of the wastewater, and simultaneously adjusts the property of the wastewater to ensure that the wastewater meets the requirements of the subsequent process;
(4) the effluent of the oxidation unit is sent to a biodegradation unit; the large carbon chain organic matter obtained by the preliminary degradation of the wastewater through the oxidation unit is further degraded into small carbon chain and single carbon chain organic matter, and finally converted into water, carbon dioxide and other small molecular inorganic matters; the biochemical reactions of oxidation and reduction in the biodegradation unit are alternately and repeatedly carried out, hexavalent chromium contained in the wastewater is reduced into precipitate of trivalent chromium, the precipitate is deposited at the bottom of the biodegradation unit, and the precipitate is periodically discharged;
(5) and (3) sending the effluent of the biodegradation unit into a post-filtering unit, removing redundant impurities in the wastewater, and then discharging the wastewater after reaching the standard and directly recycling the wastewater or recycling the wastewater after advanced treatment.
The filter medium in the primary filter unit is one or a combination of a plurality of porous filter media, granular filter media and alloy screens; wherein the porous filter medium is ceramic or nylon, and the filter aperture is 30-50 μm; the granular filter medium is one or two of manganese sand or quartz sand.
In the heterogeneous catalytic oxidation process in the oxidation unit, the catalyst adopts one or more of platinum, lead, nickel and copper oxides, and is sintered into a net-shaped or granular structure at high temperature; the oxidant is air or ozone.
The biodegradation unit is a full-flow anaerobic biodegradation process and comprises 2 process sections of a hydrolytic acidification section and an anaerobic digestion section; in the hydrolysis acidification section, large carbon chain organic matters contained in the wastewater are converted into small carbon chain hydrocarbon compounds, and a plurality of organic acids are contained in the products; in an acidic environment, hexavalent chromium in the wastewater is used as an electron acceptor, and the biological strain takes small carbon chain molecules as an electron donor to reduce the hexavalent chromium into trivalent chromium; in the anaerobic biological section, low-valence chromium ions generated by the reaction of the hydrolytic acidification section are combined with OH < - > in the wastewater in a weak alkali environment by means of metabolism of anaerobic biological strains to form low-valence chromium precipitates which are gradually separated from the wastewater; meanwhile, the small carbon chain organic pollutants are metabolized by the biological strains and finally converted into water, carbon dioxide and other inorganic substances; meanwhile, ammonia nitrogen and total phosphorus are also removed.
And the low-valence chromium precipitate is separately collected and used as a metal chromium smelting raw material.
The filtering medium in the post-filtering unit is one or more of quartz sand, anthracite, activated carbon, magnetite, manganese sand, ceramsite and porous ceramic, and the particle size of the filtering medium is 0.5-5 mm.
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.
[ examples ] A method for producing a compound
In the embodiment, the high-concentration COD chromium-containing electroplating cleaning wastewater is cleaning wastewater generated by cleaning and degreasing the surface of a roller to be electroplated from a certain enterprise, the wastewater contains 3500mg/L of oil, 3000mg/L of COD, 16.1mg/L of ammonia nitrogen, 53.9mg/L of total phosphorus, 0.96mg/L of hexavalent chromium, 1.77mg/L of total chromium and 9.73 of pH value, and meanwhile, the wastewater contains a large amount of iron ions.
The wastewater is firstly sent into a regulating tank for homogenizing and equalizing, and then sent into a primary filtering unit to remove large-particle insoluble impurities in the wastewater. The filter medium in the primary filter unit is aluminum silicate ceramic, and the filter pore size is 30 mu m. The filtration speed is not changed in the filtration operation, and the wastewater quickly passes through the filtration layer.
The effluent of the primary filtering unit is sent into an oxidation unit, solid fillers made of various non-metal materials such as nylon 66, PE, cobblestone, clay particles and the like are arranged in the oxidation unit, a catalyst is an alloy oxide of platinum, lead, nickel and copper, and oxygen in the air is used as an oxidant. Under the ambient conditions of normal temperature and normal pressure, the wastewater is fully contacted and reacted with oxygen, and the large carbon chains of oil molecules are broken to form organic carbon chains with different sizes.
The wastewater after chain breaking enters a subsequent biodegradation unit, and carbon chains of organic matters in the wastewater are further degraded until the wastewater is subjected to chain breakingFinal formation of H2O and CO2. After the wastewater passes through the hydrolytic acidification section and the anaerobic nitrification section in sequence, the effluent is sent to the post-filtration unit.
The rear filtering unit is used for removing redundant impurities in the wastewater, the filtering medium is selected from manganese sand with the particle size of 0.5-4 mm, quartz sand with the particle size of 0.5-1.2 mm and active carbon with the particle size of 0.8-1.8 mm, and the manganese sand, the quartz sand and the active carbon are laid from bottom to top in sequence.
In the embodiment, the COD of the treated effluent is less than or equal to 30mg/L, the ammonia nitrogen is less than or equal to 2mg/L, the total phosphorus is less than or equal to 1mg/L, the hexavalent chromium is less than or equal to 0.02mg/L, the total chromium is less than or equal to 0.03mg/L, the pH value is 7.80, the water quality standard of reuse water is met, and the treated effluent can be used as makeup water for a cleaning tank for reuse.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A combined biological treatment method of high-concentration COD chromium-containing electroplating cleaning wastewater is characterized in that the COD concentration in the electroplating cleaning wastewater is more than or equal to 2000mg/L, and the concentration of hexavalent chromium is less than or equal to 10 mg/L; the processing method comprises the following steps:
(1) firstly, feeding the wastewater into a regulating tank, and homogenizing;
(2) the effluent of the regulating reservoir is sent into a primary filtering unit to remove large-particle insoluble impurities in the wastewater;
(3) the effluent of the primary filtering unit is sent into an oxidizing unit; the oxidation unit adopts heterogeneous catalytic oxidation, carries out chain scission on complex organic pollutants in the wastewater under the action of a catalyst at normal temperature and normal pressure, improves the biodegradability of the wastewater, and simultaneously adjusts the property of the wastewater to ensure that the wastewater meets the requirements of the subsequent process;
(4) the effluent of the oxidation unit is sent to a biodegradation unit; the large carbon chain organic matter obtained by the preliminary degradation of the wastewater through the oxidation unit is further degraded into small carbon chain and single carbon chain organic matter, and finally converted into water, carbon dioxide and other small molecular inorganic matters; the biochemical reactions of oxidation and reduction in the biodegradation unit are alternately and repeatedly carried out, hexavalent chromium contained in the wastewater is reduced into precipitate of trivalent chromium, the precipitate is deposited at the bottom of the biodegradation unit, and the precipitate is periodically discharged;
(5) and (3) sending the effluent of the biodegradation unit into a post-filtering unit, removing redundant impurities in the wastewater, and then discharging the wastewater after reaching the standard and directly recycling the wastewater or recycling the wastewater after advanced treatment.
2. The combined biological treatment method for the high-concentration COD chromium-containing electroplating cleaning wastewater according to claim 1, characterized in that the filter medium in the primary filter unit is one or more of porous filter medium, granular filter medium and alloy screen; wherein the porous filter medium is ceramic or nylon, and the filter aperture is 30-50 μm; the granular filter medium is one or two of manganese sand or quartz sand.
3. The combined biological treatment method for the high-concentration COD chromium-containing electroplating cleaning wastewater according to claim 1, characterized in that in the heterogeneous catalytic oxidation process in the oxidation unit, the catalyst adopts one or more oxides of platinum, lead, nickel and copper, and is sintered into a net-shaped or granular structure at high temperature; the oxidant is air or ozone.
4. The combined biological treatment method for the high-concentration COD chromium-containing electroplating cleaning wastewater according to claim 1, characterized in that the biodegradation unit is a full-flow anaerobic biodegradation process comprising 2 process sections of a hydrolytic acidification section and an anaerobic digestion section;
in the hydrolysis acidification section, large carbon chain organic matters contained in the wastewater are converted into small carbon chain hydrocarbon compounds, and a plurality of organic acids are contained in the products; in an acidic environment, hexavalent chromium in the wastewater is used as an electron acceptor, and the biological strain takes small carbon chain molecules as an electron donor to reduce the hexavalent chromium into trivalent chromium;
in the anaerobic biological section, low-valence chromium ions generated by the reaction of the hydrolytic acidification section are combined with OH < - > in the wastewater in a weak alkali environment by means of metabolism of anaerobic biological strains to form low-valence chromium precipitates which are gradually separated from the wastewater; meanwhile, the small carbon chain organic pollutants are metabolized by the biological strains and finally converted into water, carbon dioxide and other inorganic substances; ammonia nitrogen and total phosphorus are also removed.
5. The combined biological treatment method of high concentration COD chromium containing electroplating cleaning waste water according to claim 4, characterized in that the low valence state chromium precipitate is collected separately and used as metallic chromium smelting raw material.
6. The combined biological treatment method of high concentration COD chromium containing electroplating cleaning wastewater according to claim 1, characterized in that the filtering medium in the post-filtering unit is one or more of quartz sand, anthracite, activated carbon, magnetite, manganese sand, ceramsite and porous ceramic, and the particle size of the filtering medium is 0.5-5 mm.
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| CN111606519A (en) * | 2020-06-09 | 2020-09-01 | 闫娟 | Advanced treatment method for electroplating wastewater |
| CN113135642A (en) * | 2021-05-25 | 2021-07-20 | 西安泰瑞环保技术有限公司 | Copper foil passivation solution wastewater treatment process |
| CN115432890A (en) * | 2022-09-21 | 2022-12-06 | 无锡市道格环保科技有限公司 | Treatment device and method for reducing pollutant discharge in chromium-containing metal ion wastewater |
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| CN113135642A (en) * | 2021-05-25 | 2021-07-20 | 西安泰瑞环保技术有限公司 | Copper foil passivation solution wastewater treatment process |
| CN115432890A (en) * | 2022-09-21 | 2022-12-06 | 无锡市道格环保科技有限公司 | Treatment device and method for reducing pollutant discharge in chromium-containing metal ion wastewater |
| CN115432890B (en) * | 2022-09-21 | 2024-01-23 | 无锡市道格环保科技有限公司 | Treatment device and method for reducing pollutant emission in chromium-containing metal ion wastewater |
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