CN112028382A - Heavy metal acidic wastewater treatment system and treatment method - Google Patents
Heavy metal acidic wastewater treatment system and treatment method Download PDFInfo
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- CN112028382A CN112028382A CN202010644306.6A CN202010644306A CN112028382A CN 112028382 A CN112028382 A CN 112028382A CN 202010644306 A CN202010644306 A CN 202010644306A CN 112028382 A CN112028382 A CN 112028382A
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- 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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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- 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
- C02F1/5281—Installations for water purification using chemical agents
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/70—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
Abstract
The invention provides a heavy metal acidic wastewater treatment system which comprises a primary filtering part, a replacement part, a pH adjusting tank, a reduction treatment part and a biochemical treatment part which are sequentially connected, wherein the reduction treatment part comprises a first reduction part and a second reduction part which are arranged in the same way, the upper part of the side wall of the first reduction part is fixedly provided with a water inlet pipe, the lower part of the side wall of the first reduction part is fixedly provided with a water outlet pipe which can be opened and closed, the water outlet pipe is provided with a filter screen, the upper part of the first reduction part is provided with a gas through port which can be opened and closed, the gas through port is externally connected with an inflating device or a gas collecting device, the bottom of the first reduction part is provided with a heating tank, a plurality of filter plates are arranged in the first reduction part, the filter plates are horizontally arranged or. The invention can efficiently remove heavy metal and sulfate ions in the acid wastewater polluted by heavy metal through the synergistic effect of the whole system.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment in environmental protection, and particularly relates to a heavy metal acidic wastewater treatment system and a heavy metal acidic wastewater treatment method.
Background
The heavy metal wastewater is wastewater containing heavy metals discharged in the industrial production processes of mining and metallurgy, mechanical manufacturing, chemical industry, electronics, instruments and the like. Mainly refers to heavy metals such as arsenic, lead, zinc, chromium, cobalt, cadmium, nickel, mercury, copper and the like. After the heavy metal enters the water body, the heavy metal has an amplification effect on a food chain, and can be accumulated in certain organs of a human body to cause poisoning and harm the health of the human body. Heavy metals in wastewater generally cannot be decomposed and destroyed, and only can be transferred to the existing position and converted into the physical and chemical forms. The treatment method comprises the treatment of a chemical precipitation method, an adsorption method, a reduction method, a membrane separation method, an ion exchange method, a coagulation method and the like, and the heavy metals in the treated water can be discharged or recycled when the heavy metals are lower than the discharge standard.
The sponge iron is also called Direct Reduced Iron (DRI), the main active ingredients (more than or equal to 97 percent) of the DRI are completely consistent with common reductive iron powder, the DRI is simple substance iron or zero-valent iron, but the DRI has extremely high porosity, large specific surface area and high reduction activity, is a high-efficiency water treatment deoxidant, has good removal performance on pollutants such as organic matters, heavy metals, inorganic salts and the like in a water body, and is a zero-valent iron material with great potential.
The vibrio desulfurizating bioremediation technology is applied to industrial wastewater polluted by certain heavy metals and sulfate radicals, namely, the vibrio desulfurizating is utilized to carry out dissimilatory reduction and metabolism on sulfate radical ions into hydrogen sulfide under the anaerobic condition, and the hydrogen sulfide is combined with the heavy metals in the wastewater to generate insoluble metal sulfide precipitates for removing the insoluble metal sulfide precipitates.
The invention patent CN 106115932B discloses a method for removing sulfate and Cr (VI) wastewater by the synergy of sponge iron and microorganisms; under the anaerobic condition, sponge iron solution A, bacterial suspension B of sulfate reducing bacteria and bacterial suspension C of iron reducing bacteria are mixed according to the volume ratio of 1: 1: 1-1: 3: 4, mixing, aging for 30-60 min, repeatedly washing sponge iron/microbial microspheres by using deoxidized deionized water after the reaction is finished, and soaking in sterile normal saline; obtaining a mixture of sponge iron and sulfate reducing bacteria/iron reducing bacteria; the obtained mixture of the sponge iron and the sulfate reducing bacteria/iron reducing bacteria is mixed with sulfate and Cr (VI) wastewater, and reacts for more than 24 hours at normal temperature, and simultaneously sulfate and Cr (VI) in the wastewater are purified. The method has the advantages that the removal rate of Cr (VI) metal reaches more than 89 percent, the required equipment is simple, the reaction is finished at normal temperature and normal pressure, the product is a solid phase, the reaction system is a liquid phase, and the product is easy to separate and is used for large-scale industrial production. The invention discloses a method for reducing sulfate radicals of iron sulfate, which is characterized in that sulfate reducing bacteria and iron reducing bacteria are simultaneously loaded on sponge iron, and the reduction effect of the sponge iron is weakened after the sponge iron is changed in the process of reducing sulfate radicals.
The invention patent CN 104071975B discloses a treatment device and a treatment method for mine heavy metal acidic wastewater, wherein the treatment device realizes the flow of liquid among a sedimentation tank, a reduction device, a desulfurization device, a PRB device and a pH adjusting tank through a pump system and a water guide pipe system, and realizes the reduction of sulfate in wastewater, the desulfurization treatment of wastewater, the removal of heavy metal pollution and the pH adjustment of wastewater. The method has the advantages of simple process, simple operation, low cost and high efficiency, can realize the large-scale and engineering application of the treatment of the acid wastewater polluted by the heavy metals in the mine, effectively avoids the generation of secondary pollution in the pollution treatment process because pollutants in the whole process flow are in a relatively closed space, can be widely applied to the safe treatment of the acid wastewater polluted by the heavy metals in different types of mines, and can effectively remove the pollution of the heavy metals such as arsenic, lead, copper, zinc, chromium, cadmium and the like in the wastewater. The reduction device in the invention patent is only used for removing sulfate in wastewater, heavy metal is removed by utilizing a PRB (permeable reactive barrier) device, the size of the reactive barrier is determined according to the size of water quantity to be treated, and the higher the surface price is, the higher the manufacturing cost is.
Disclosure of Invention
In order to overcome the problems in the prior art, the application provides a heavy metal acidic wastewater treatment system and a treatment method.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the utility model provides a heavy metal acid wastewater treatment system, includes consecutive filtration portion, replacement portion, pH equalizing basin for the first time, reduction processing portion and biochemical treatment portion, be connected through the pipeline between filtration portion, replacement portion, pH equalizing basin, reduction processing portion and the biochemical treatment portion for the first time, be equipped with the elevator pump on each connecting tube.
The reduction treatment portion comprises a first reduction portion and a second reduction portion which are arranged in the same manner, a water inlet pipe is fixedly mounted on the upper portion of the side wall of the first reduction portion, a water outlet pipe which can be opened and closed is fixedly mounted on the lower portion of the side wall of the first reduction portion, a filter screen is arranged at the position of the water outlet pipe, and the filter screen is used for filtering sponge iron entering the solution in the first reduction portion. First reduction portion upper portion is equipped with and can opens and closed gas through the mouth, external aeration equipment or gas collecting device of gas through the mouth, first reduction portion and second reduction portion need anaerobic environment, lets in high-purity nitrogen gas deoxidization through aeration equipment during the reaction, and the gas that produces after the reaction is finished collects. The bottom of the first reduction part is provided with a heating groove, a plurality of filter plates are arranged in the first reduction part, the filter plates are horizontally arranged or obliquely arranged, the filter materials of the filter plates are coupling materials of sponge iron loaded desulfurization vibrios, the water outlet pipe of the first reduction part is connected with the water inlet pipe of the second reduction part through a pipeline, and a lifting pump is arranged on the pipeline.
Further, first filter house lateral wall upper portion is provided with at least one water inlet, has the delivery port on the lateral wall lower part, the below of water inlet is provided with the filter screen, and a plurality of water inlets are intake simultaneously for even the passing through filter screen of intaking after, the large granule material in the removal waste water.
And further, an activated carbon adsorption plate is arranged below the filter screen, and the activated carbon adsorption plate is used for carrying out primary treatment on the wastewater.
Furthermore, a spray pipe is arranged on the upper portion of the replacement portion, a plurality of uniformly arranged spray head groups are arranged on the bottom wall of the spray pipe, and the spray head groups spray iron powder and are used for removing a small amount of heavy metals in the wastewater.
Further, the replacement part is provided with a first stirring device for accelerating the reaction.
Furthermore, the bottom of the replacement part is conical, and the arrangement of the conical part is favorable for the deposition of the replaced heavy metal.
Further, the bottom of the displacement part is provided with an outlet for discharging sediment from the outlet.
Further, the pH adjusting tank is connected with the medicament tank, the medicament tank adds the medicament through adding the medicine pump, the pH adjusting tank is equipped with second agitating unit. Used for adding the regulating agent and then uniformly stirring.
Furthermore, first reduction portion and second reduction portion all are equipped with detection device, detection device includes one or several kinds in temperature detector, oxygen concentration detector, the pH value detector for the temperature of monitoring reduction processing portion, oxygen concentration and waste water pH value.
The heavy metal acidic wastewater treatment method is characterized by comprising the following steps:
s1, after primary filtration, adding iron powder for replacement reaction, and obtaining upper liquid and sediment after sedimentation;
s2, adjusting the pH of the upper layer liquid obtained in the step S1 to be neutral, and then treating the upper layer liquid by using a coupling material of sponge iron loaded desulfurization vibrio, wherein the reaction temperature is 20-37 ℃, and heavy metals in the upper layer liquid are removed;
s3, treating the liquid treated in the step S2 by using the coupling material of the sponge iron-loaded desulfurization vibrio, wherein the reaction temperature is 20-37 ℃, and sulfate ions in the liquid are removed;
and S4, performing biochemical treatment on the liquid processed in the step S3 to remove organic matters in the liquid.
Further, the time for the replacement reaction in the step S1 is 6-12h, and the time for the reaction with the coupling material of the sponge iron-loaded vibrio desulfurizati in the steps S2 and S3 is 12-24 h.
Further, the volume ratio of the sponge iron solution to the desulfurization vibrio suspension in the logarithmic growth phase in the coupling material of the sponge iron-loaded desulfurization vibrio is 1: 1-5.
The working principle is as follows: heavy metal acid wastewater contains heavy metal, a large amount of sulfate ions and other substances, iron powder in the replacement part not only replaces a part of heavy metal ions, but also reacts with hydrogen ions in the wastewater to generate hydrogen, so that the acidity of the wastewater is reduced, the acidity environment is eliminated, the reaction of vibrio desulfurization is more facilitated, and the pH of the wastewater treated by the replacement part can be adjusted to be neutral mainly by a small amount of adjusting reagent.
The sponge iron has a porous internal structure and a large specific surface area, the number of the loaded desulfurization vibrios is large, the desulfurization vibrios reduce sulfate radicals into divalent sulfides under the anaerobic condition, and the sponge iron has the reduction activity to reduce heavy metals and then react with S2-The reaction produces a sulfide precipitate. Iron oxides such as Fe generated on the surface of the sponge iron after the sponge iron reduces heavy metals2O3FeOOH and Fe3O4And the like are adsorbed on the surface of the sponge iron, so that a large amount of sulfate ions can not be completely removed, the sponge iron is treated by using the coupling material of the desulfurization vibrio loaded on the sponge iron again to remove residual heavy metal and sulfate, and finally, the residual organic substances are treated by using the existing anaerobic-anoxic-aerobic biochemical treatment system.
The invention has the following beneficial effects:
the first reduction part can remove the residual heavy metal and partial sulfate radical after being replaced by iron powder, wherein the coupling material of the sponge iron loaded desulfurization vibrio is arranged in a filter plate mode and is obliquely arranged, so that the contact area of the waste water and the coupling material can be increased, and compared with the method that the waste water is directly added into the solution of the coupling material of the sponge iron loaded desulfurization vibrio, the heavy metal can be better removed; after the sponge iron is reduced with heavy metal,iron oxides such as Fe generated on the surface thereof2O3FeOOH and Fe3O4When the heavy metal sulfate is adsorbed on the surface of the sponge iron, a large amount of sulfate ions cannot be completely removed, so that the second reduction part can be used for removing the residual heavy metal and most of the residual sulfate after passing through the first reduction part, the water-insoluble sulfide is generated and then removed, and the gas generated in the reaction process is collected and then treated, so that the environment is not polluted.
The present application provides a substituted part that reacts with iron powder, and has the following effects: (1) the heavy metal (such as copper) in the wastewater, which reacts preferentially with the iron powder, is replaced by the replacement of the iron powder, so that the treatment burden of the coupling material of the subsequent sponge iron-loaded desulfurization vibrio is reduced; (2) the acid wastewater contains a large amount of H+After the iron powder is added, the hydrogen ions in the wastewater can be eliminated, pollution-free hydrogen is generated, and the acidity of the wastewater is reduced; (3) the acidic wastewater is not beneficial to the growth of the vibrio desulfurizating, and after the iron powder is added for elimination, the wastewater can be adjusted to be neutral by only adding a small amount of adjusting agent, so that the using amount of the adjusting agent is saved, and a foundation is laid for the next step of treatment by utilizing a sponge iron loaded vibrio desulfurizating coupling system.
The application efficiently removes heavy metal and sulfate radical in the acidic heavy metal wastewater through a replacement and reduction treatment process, and after the heavy metal and the sulfate radical are biologically treated and become pollution-free substances, the heavy metal and the sulfate radical can be safely discharged.
Drawings
FIG. 1 is a schematic diagram of a processing system according to the present application;
reference numerals
1. A filtering part; 2. a replacement section; 3. a pH adjusting tank; 4. a reduction processing unit; 5. a biochemical treatment section; 6. a lift pump;
11. a water inlet; 12. a water outlet; 13. filtering with a screen; 14. an activated carbon mesh;
21. a spray tube; 22. a nozzle group; 23. an outlet; 24. a first stirring device;
31. a medicament pool; 32. a dosing pump; 33. a second stirring device;
41. a first reduction part; 42. a second reduction part;
411. a water inlet pipe; 412. a water outlet pipe; 413. a gas passage port; 414. a heating tank; 415. a filter plate; 416. the sponge iron is loaded with a coupling material of the desulfurization vibrio.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
1. Heavy metal acid wastewater treatment system
The utility model provides a heavy metal acid wastewater treatment system, including first filter house 1, replacement portion 2, pH equalizing basin 3, reduction treatment portion 4 and biochemical treatment portion 5, wherein first filter house 1, replacement portion 2, pH equalizing basin 3, reduction treatment portion 4 and biochemical treatment portion 5 loop through the pipeline and are connected, be equipped with elevator pump 6 on each connecting tube, in this embodiment, concrete connected mode is that the lower part of first filter house 1 links to each other with replacement portion 2's upper portion, replacement portion 2's lower part links to each other with pH equalizing basin 3's upper portion, pH equalizing basin 3's lower part links to each other with reduction treatment portion 4's upper portion, reduction treatment portion 4's upper portion with biochemical treatment portion 5's upper portion links to each other, is connected through corrosion-resistant pipeline between each device, convey through corrosion-resistant elevator pump 6.
1 lateral wall upper portion of first filter portion is provided with at least one water inlet 11, has delivery port 12 on the lateral wall lower part, and the below of water inlet 11 is provided with filter screen 13 for get rid of the large granule impurity in the waste water, the below of filter screen 13 is equipped with activated carbon adsorption plate 14, carries out waste water preliminary treatment back through activated carbon adsorption plate 14, and waste water gets into replacement portion 2 from first filter portion 1 discharge.
The pH adjusting tank 3 is connected with a chemical tank 31, the chemical tank 31 is added with chemicals by a chemical adding pump 32 and is used for adjusting the wastewater to be neutral, the specific pH adjustment is 6-8, the pH adjusting tank 3 is provided with a second stirring device 33, preferably, a pH detection device (not shown in the figure) is arranged to monitor the liquid, and the wastewater discharged from the pH adjusting tank enters the reduction treatment part 4.
The reduction treatment part 4 comprises a first reduction part 41 and a second reduction part 42 which are arranged in the same way, the upper part of the side wall of the first reduction part 41 is fixedly provided with a water inlet pipe 411, the lower part of the side wall of the first reduction part is fixedly provided with a water outlet pipe 412 which can be opened and closed, and the position of the water outlet pipe 412 is provided with a filter screen (not shown in the figure) to prevent sponge iron in the wastewater from being discharged along the water flow.
The upper part of the first reduction part 41 is provided with an openable and closable gas passing port 413, the gas passing port 413 is externally connected with an inflating device or a gas collecting device, nitrogen is filled through the gas passing port 413 to remove oxygen in a container and dissolved oxygen in liquid, so that the anaerobic environment of reaction is ensured, and after the reaction is finished, gas generated by the reaction is collected through the gas passing port 413 to perform other treatment.
The bottom of the first reduction part 41 is provided with a heating tank 414, the first reduction part 41 is internally provided with a plurality of filter plates 415, wherein the filter plates 415 are horizontally arranged or obliquely arranged, in the embodiment, the filter plates 415 are obliquely arranged, in other embodiments, the filter plates 415 can also be obliquely arranged and horizontally arranged to be combined, the filter materials of the filter plates 415 are sponge iron loaded with coupling materials 416 of desulfurization vibrios, the water outlet pipe 412 of the first reduction part 41 is connected with the water inlet pipe of the second reduction part 42 through a pipeline, and the pipeline is provided with a lift pump for lifting wastewater.
The first reduction part 41 is also internally provided with a temperature detector, an oxygen concentration detector and a pH value detector, which are used for detecting the temperature of the wastewater, the oxygen concentration in the container and the pH value of the wastewater, and provide a suitable environment for the coupling system of the sponge iron loaded desulfurization vibrio.
The vibrio desulfurizate in the embodiment is a vibrio desulfurizate purchased from a Chinese common microorganism strain preservation management center (Yangyang district, Beijing, China, zip 100101, No. 1.3469), and bacteria in logarithmic growth phase are taken to prepare into bacterial suspension after amplification culture.
The biochemical treatment part 5 is used for degrading organic matters in the wastewater, and the biochemical treatment part adopts the existing anaerobic-anoxic-aerobic biochemical treatment system to treat the residual organic matters and discharges the organic matters after the organic matters are qualified.
2. Heavy metal acidic wastewater treatment method
Collecting acid wastewater polluted by heavy metal in a certain mine in Hunan, and detecting the pH value and SO of the wastewater before treatment4 2-And the concentrations of the copper, zinc, cadmium and lead components.
Example 1
(1) Removing large-particle impurities from the acidic wastewater after preliminary filtration, adding iron powder, stirring and reacting for 6 hours, and standing to obtain upper-layer liquid and precipitate;
(2) mixing a sponge iron solution and a vibrio desulfurizate suspension according to a volume ratio of 1:1 to prepare a coupling system of the sponge iron solution loaded with the vibrio desulfurizate suspension, adjusting the pH of the upper layer liquid obtained in the step 1 to be neutral, and treating the upper layer liquid for 12 hours by using a coupling material at a reaction temperature of 37 ℃ to remove the residual heavy metal ions in the upper layer liquid;
(3) treating the liquid treated in the step 2 for 12 hours by using a coupling material of a sponge iron solution and a desulfurization vibrio suspension again, wherein the reaction temperature is 37 ℃, and removing sulfate ions in the liquid;
(4) and (4) performing biochemical treatment on the liquid treated in the step (3) to remove organic matters in the liquid.
Example 2
(1) Removing large-particle impurities from the acidic wastewater after preliminary filtration, adding iron powder, stirring and reacting for 10 hours, and standing to obtain upper-layer liquid and precipitate;
(2) mixing a sponge iron solution and a vibrio desulfurizate suspension according to a volume ratio of 1:3 to prepare a coupling system of the sponge iron solution loaded with the vibrio desulfurizate suspension, adjusting the pH of the upper layer liquid obtained in the step 1 to be neutral, and treating the upper layer liquid for 20 hours by using a coupling material at a reaction temperature of 37 ℃ to remove the residual heavy metal ions in the upper layer liquid;
(3) treating the liquid treated in the step 2 for 20 hours by using a coupling material of a sponge iron solution and a desulfurization vibrio suspension again, wherein the reaction temperature is 37 ℃, and removing sulfate ions in the liquid;
(4) and (4) performing biochemical treatment on the liquid treated in the step (3) to remove organic matters in the liquid.
Example 3
(1) Removing large-particle impurities from the acidic wastewater after preliminary filtration, adding iron powder, stirring and reacting for 12 hours, and standing to obtain upper-layer liquid and precipitate;
(2) mixing a sponge iron solution and a vibrio desulfurizate suspension according to a volume ratio of 1:5 to prepare a coupling system of the sponge iron solution loaded with the vibrio desulfurizate suspension, adjusting the pH of the upper layer liquid obtained in the step 1 to be neutral, and treating the upper layer liquid for 24 hours by using a coupling material at a reaction temperature of 30 ℃ to remove the residual heavy metal ions in the upper layer liquid;
(3) treating the liquid treated in the step 2 for 24 hours by using a coupling material of a sponge iron solution and a desulfurization vibrio suspension again, wherein the reaction temperature is 30 ℃, and removing sulfate ions in the liquid;
(4) and (4) performing biochemical treatment on the liquid treated in the step (3) to remove organic matters in the liquid.
Comparative example 1
(1) Primarily filtering the acidic wastewater to remove large-particle impurities.
(2) Mixing a sponge iron solution and a vibrio desulfurizate suspension according to a volume ratio of 1:2 to prepare a coupling system of the sponge iron solution loaded with the vibrio desulfurizate suspension, adjusting the pH of the liquid obtained in the step 1 to be neutral, and treating the liquid for 12 hours by using the coupling system to remove the residual heavy metal ions in the upper layer of liquid;
(3) treating the liquid treated in the step 2 for 12 hours by using a coupling system of the sponge iron solution and the vibrio desulfurizate suspension again, and removing sulfate ions in the liquid;
(4) and (4) performing biochemical treatment on the liquid treated in the step (3) to remove organic matters in the liquid.
Comparative example 2
(1) Removing large-particle impurities from the acidic wastewater after preliminary filtration, adding iron powder, stirring for reaction for 6 hours, and standing to obtain upper-layer liquid and precipitate;
(2) mixing a sponge iron solution and a vibrio desulfurizate suspension according to a volume ratio of 1:2 to prepare a coupling system of the sponge iron solution loaded with the vibrio desulfurizate suspension, adjusting the pH of the upper layer liquid obtained in the step 1 to be neutral, and treating the upper layer liquid for 24 hours by using the coupling system to remove the residual heavy metal ions in the upper layer liquid;
(3) and (4) performing biochemical treatment on the liquid treated in the step (3) to remove organic matters in the liquid.
3. Removal Rate detection
The pH value and SO of the water after the treatment of examples 1-3 and comparative examples 1-24 2-And the concentration of each component of copper, zinc, cadmium and lead, wherein the pH is detected by a pH meter, and SO is detected4 2-Detecting by ion chromatography, detecting heavy metal by atomic absorption spectrophotometry, and averaging the three results.
The results of comparison between before and after treatment are shown in Table 1 with reference to the Standard for the quality of Water on the surface (GB 3838-2002).
TABLE 1
Example 1 compared with comparative example 1, in comparative example 1, the replacement process was not performed using iron powder, and it can be seen from table 1 that the removal capacity of heavy metals in comparative example 1 is reduced by about 20-30% compared to examples 1-3. In comparative example 2, in order to set the sponge iron-loaded desulfurization vibrio coupling system for treatment for 24 hours, compared with the treatment for 12 hours in example 1, the heavy metal removal capacity is greatly reduced, especially the SO removal capacity is greatly reduced4 2-The removal capacity is analyzed due to the iron oxides such as Fe generated on the surface of the sponge iron after the sponge iron reduces heavy metals2O3And Fe3O4And the like are adsorbed on the surface of the sponge iron. The acidity of the wastewater is improved after the pH value of the wastewater is treated.
The principle of the invention is as follows: removing large particle impurities from the wastewater after primary filtration, replacing a part of heavy metals in the solution by using iron powder, simultaneously removing hydrogen ions in the wastewater by using the iron powder, reducing the acidity of the wastewater, adjusting the wastewater with the reduced acidity into a neutral condition meeting the growth of vibrio desulfurizati after the pH of a small dose of medicament is adjusted, wherein the sponge iron has a porous internal structure and a large specific surface area, and is loaded with a large number of vibrio desulfurizati, and the vibrio desulfurizati reduces sulfate radicals into divalent sulfides under the anaerobic condition, so that the heavy metal ions and a small part of sulfate radicals are removed from a coupling system of the vibrio desulfurizati loaded with the sponge iron in the first reduction part, and the heavy metal ions are reduced by the reduction activity of the sponge iron2-The reaction produces a sulfide precipitate. Iron oxides such as Fe generated on the surface of the sponge iron after the sponge iron reduces heavy metals2O3And Fe3O4And the heavy metal ions and most of the residual sulfate radicals are further removed in the coupling system of the sponge iron loaded desulfurization vibrio in the second reduction part, and finally, other organic substances and the like are removed from the wastewater through biochemical treatment.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and is not intended to limit the practice of the invention to these embodiments. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. The heavy metal acid wastewater treatment system is characterized by comprising a primary filtering part, a displacement part, a pH adjusting tank, a reduction treatment part and a biochemical treatment part which are sequentially connected, wherein the primary filtering part, the displacement part, the pH adjusting tank, the reduction treatment part and the biochemical treatment part are connected through pipelines, and each connecting pipeline is provided with a lifting pump;
the reduction processing part comprises a first reduction part and a second reduction part which are arranged identically, a water inlet pipe is fixedly mounted on the upper portion of the side wall of the first reduction part, a water outlet pipe which can be opened and closed is fixedly mounted on the lower portion of the side wall of the first reduction part, a filter screen is arranged at the position of the water outlet pipe, a gas passing port which can be opened and closed is arranged on the upper portion of the first reduction part, an external inflation device or a gas collecting device of the gas passing port is arranged on the gas passing port, a heating groove is formed in the bottom of the first reduction part, a plurality of filter plates are arranged in the first reduction part, the filter plates are horizontally arranged or obliquely arranged, a filter material of the filter plates is a coupling material of sponge iron loaded desulfurization vibrios, the water outlet pipe of the first reduction part is.
2. The heavy metal acid wastewater treatment system according to claim 1, wherein at least one water inlet is arranged on the upper portion of the side wall of the primary filtering part, a water outlet is arranged on the lower portion of the side wall, a filter screen is arranged below the water inlet, an activated carbon adsorption plate is arranged below the filter screen, medium and large particle impurities in the wastewater are removed through the filter screen, and the wastewater primary treatment is carried out through the activated carbon adsorption plate.
3. The heavy metal acid wastewater treatment system of claim 1, wherein a spray pipe is arranged at the upper part of the displacement part, a plurality of uniformly arranged spray head groups are arranged on the bottom wall of the spray pipe, and the spray head groups spray iron powder for removing a small amount of heavy metal in wastewater.
4. The heavy metal acid wastewater treatment system according to claim 1, wherein the displacement section is provided with a first stirring device for accelerating the reaction.
5. The heavy metal acid wastewater treatment system of claim 1, wherein the bottom of the displacement part is conical, and an outlet is formed at the bottom of the displacement part.
6. The heavy metal acid wastewater treatment system of claim 1, wherein the pH adjusting tank is connected with a reagent tank, the reagent tank is used for adding reagents through a reagent adding pump, and the pH adjusting tank is provided with a second stirring device.
7. The heavy metal acid wastewater treatment system according to claim 1, wherein the first reduction part and the second reduction part are provided with detection devices, and the detection devices comprise one or more of a temperature detector, an oxygen concentration detector and a pH value detector.
8. The heavy metal acidic wastewater treatment method is characterized by comprising the following steps:
s1, after primary filtration, adding iron powder for replacement reaction, and obtaining upper liquid and sediment after sedimentation;
s2, adjusting the pH of the upper layer liquid obtained in the step S1 to be neutral, and then treating the upper layer liquid by using a coupling material of sponge iron loaded desulfurization vibrio, wherein the reaction temperature is 20-37 ℃, and heavy metals in the upper layer liquid are removed;
s3, treating the liquid treated in the step S2 by using the coupling material of the sponge iron-loaded desulfurization vibrio, wherein the reaction temperature is 20-37 ℃, and sulfate ions in the liquid are removed;
and S4, performing biochemical treatment on the liquid processed in the step S3 to remove organic matters in the liquid.
9. The method for treating heavy metal acidic wastewater according to claim 1, wherein the time for the shift reaction in step S1 is 6-12 hours, and the time for the reaction with the coupling material of the sponge iron-loaded vibrio devulcani in steps S2 and S3 is 12-24 hours.
10. The method for treating heavy metal acidic wastewater according to claim 1, wherein the volume ratio of the sponge iron solution to the desulfurization vibrio suspension in logarithmic growth phase in the coupling material of the sponge iron-loaded desulfurization vibrio is 1: 1-5.
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