CN110373544A - A kind of Deep-Sea Microorganisms gradient handles the device and method of metal ion in heavy metal sewage sludge - Google Patents
A kind of Deep-Sea Microorganisms gradient handles the device and method of metal ion in heavy metal sewage sludge Download PDFInfo
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- CN110373544A CN110373544A CN201910677229.1A CN201910677229A CN110373544A CN 110373544 A CN110373544 A CN 110373544A CN 201910677229 A CN201910677229 A CN 201910677229A CN 110373544 A CN110373544 A CN 110373544A
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- 244000005700 microbiome Species 0.000 title claims abstract description 61
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 60
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000010801 sewage sludge Substances 0.000 title abstract 2
- 239000002351 wastewater Substances 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000010802 sludge Substances 0.000 claims abstract description 85
- 230000003750 conditioning effect Effects 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 34
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000002386 leaching Methods 0.000 claims abstract description 7
- 230000000813 microbial effect Effects 0.000 claims description 161
- 230000003197 catalytic effect Effects 0.000 claims description 156
- 239000007788 liquid Substances 0.000 claims description 70
- 230000001580 bacterial effect Effects 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 238000005086 pumping Methods 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 20
- 241000894006 Bacteria Species 0.000 claims description 18
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000000969 carrier Substances 0.000 claims description 4
- 230000009347 mechanical transmission Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 description 39
- 150000003839 salts Chemical class 0.000 description 20
- 150000002500 ions Chemical class 0.000 description 16
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- 239000002131 composite material Substances 0.000 description 7
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- 206010021143 Hypoxia Diseases 0.000 description 6
- 230000007954 hypoxia Effects 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 229910052927 chalcanthite Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- -1 Cr6+To form metal compound Chemical class 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Removal Of Specific Substances (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses metal ion device and method in a kind of Deep-Sea Microorganisms gradient processing heavy metal sewage sludge, described device is mainly made of Leaching of Heavy Metals system and heavy metal reduction enrichment system.Leaching of Heavy Metals system includes: sludge conditioning tank, agitating device, sludge lifting pump, vacuum pump, lautertuns.Heavy metal restores enrichment system by reservoir, water pump, circulating pump, level-one microorganism catalysis reactor, second level microorganism catalysis reactor, three-level microorganism catalysis reactor, circulatory pool, triple valve；Microorganism catalysis reactor includes: water inlet, bio-carrier, water outlet, control valve, precipitation tank.Heavy metal is reduced to simple substance or compound by the advanced treating of suitable treatment high-concentration hardly-degradable heavy metal wastewater thereby of the present invention, and processing metal ion range is big, and different metal distinguishes step recycling in each reactor.
Description
Technical Field
The invention belongs to the field of environmental protection and comprehensive resource treatment, and particularly relates to a device and a method for gradient treatment of metal ions in heavy metal sludge by deep-sea microorganisms.
Background
The sludge has high water content, is easy to rot, has complex components, contains a large amount of harmful substances such as heavy metals and the like and carcinogenic substances, and can not utilize the nutrient substances. Heavy metal pollutants are difficult to treat, and when the heavy metal pollutants are accumulated in a water body to a certain limit, serious damage is caused to a water body-aquatic plant-aquatic animal system, and the self health of human beings can be influenced by a food chain. Heavy metal wastewater is produced in many production processes in the industries of mining and metallurgy, mechanical manufacturing, chemical industry, electronics, instruments and the like, and the wastewater seriously affects the health and even the life of children and adults. Chinese patent document CN201811006285.4 discloses a method for reducing heavy metal ions in mineral processing wastewater, which comprises the steps of adding alkali into the wastewater for three times, carrying out neutralization reaction, precipitating, filtering and removing the metal ions; the method has high treatment capacity, but introduces more Na into water+Plasma, causing new environmental pollution. Chinese patent document CN 201820584240.4 discloses a heavy metal wastewater treatment device, which combines a filter and a metal precipitator to purify wastewater to a large extent, but the device is complicated, occupies a large area, consumes high energy, and has excessive concentrations of Cu and Zn ions. Chinese patent document CN108660314A discloses aThe method for recovering metal by the step method is characterized in that the metal in the sulfide ore tailings is recovered, metal elements are respectively transferred from a solid phase to a liquid phase in the form of metal ions and are recovered in the form of precipitation, the process flow is simple, the operation cost is low, but the precipitated metal is a mixed metal compound and is not separated.
Disclosure of Invention
The invention aims to provide a system and a method for gradient treatment of metal ions in heavy metal sludge by deep-sea microorganisms, wherein the method utilizes microorganisms in deep-sea hydrothermal sediments to directionally reduce heavy metal ions Cu2+、Zn2+And Cr6+To form metal compound or simple substance, depositing in each metal reactor, and recovering separately. The screened deep sea hydrothermal sediment microorganisms have strong tolerance to various metals, and the device can realize the directional circulation of wastewater and has a large concentration range of treated metals. The invention is suitable for the advanced treatment of high-concentration refractory heavy metal wastewater, and reduces heavy metals into simple substances or compounds while degrading organic matters under high-salt and neutral conditions. The method and the device are environment-friendly, good in stability and low in energy consumption, and different metals are respectively recovered in each reactor in a gradient manner. Solves the problems of low wastewater purification degree and resource waste of the conventional wastewater treatment technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a device for gradient treatment of metal ions in heavy metal sludge by deep-sea microorganisms, which comprises: a heavy metal leaching system and a heavy metal reduction and enrichment system.
The heavy metal leaching system comprises a sludge conditioning tank, a stirring device, a sludge lifting pump, a vacuum pump and a filter tank;
a stirring head of the stirring device is arranged in a conditioning tank, a sludge outlet of the conditioning tank is connected with a feed inlet of a sludge lifting pump, a discharge outlet of the sludge lifting pump is connected with a filter tank, a vacuum pump is connected to the outer side of the bottom of the filter tank to form a vacuum filtration system, and a water outlet at the bottom of the filter tank is connected with a reservoir;
the heavy metal reduction and enrichment system consists of one or more than two microbial catalytic reactors, a circulating pool, a water pump, a circulating pump and a reservoir;
the microbial catalytic reactor comprises a water inlet, a biological carrier and a water outlet; the biological carrier is arranged inside the microbial catalytic reactor; wherein,
when more than two microbial catalytic reactors are arranged, the microbial catalytic reactors are connected in series from top to bottom, the water outlet of the upper-stage microbial catalytic reactor is connected with the water inlet of the next-stage microbial catalytic reactor, and the water outlet of the last-stage microbial catalytic reactor is connected with the circulating pool;
the water pump connects the reservoir with the water inlet of the first-stage microbial catalytic reactor, and the circulating pump connects the circulating tank with the other water inlet of each stage of microbial catalytic reactor in parallel;
or,
when the microbial catalytic reactor is one, the water outlet of the microbial catalytic reactor is connected with the circulating pool, the water reservoir is connected with the water inlet of the microbial catalytic reactor by the water pump, and the circulating pool is connected with the water inlet of the microbial catalytic reactor by the circulating pump.
Further, the microbial catalytic reactor can also comprise a settling tank, and the settling tank is positioned at the outer side of the bottom of the microbial catalytic reactor. Alternatively, the settling tank is disposed opposite to the bottom of the bio-carrier.
Alternatively, the biological carrier in the microbial catalytic reactor can be graphite felt which is a material commonly used in the field of microbial fuel cells, and the biological carrier is formed by fixing multiple layers of graphite felt in the reactor.
The device according to the invention, wherein the volume of the conditioning tank is preferably 20-30m3The height between the bottom of the stirring head and the bottom of the conditioning tank is 50-90 cm.
The device according to the present invention, wherein preferably the stirring device is a conventional stirrer, such as but not limited to a paddle stirrer, and the stirring head is a stirring paddle.
The device according to the present invention, wherein when the number of the microbial catalytic reactors is two or more, the height difference between the microbial catalytic reactors of each stage is preferably 100-200 cm.
The device for gradient treatment of metal ions in heavy metal sludge by deep-sea microorganisms has the following advantages:
(1) the catalytic reactors have no mechanical transmission, realize self-flow according to the placing height difference and have low energy consumption;
(2) the problem of recycling the sludge leaching wastewater is solved;
(3) realizes the gradient recovery of heavy metals in the wastewater, and omits the flow of metal recovery and re-separation.
The invention also provides a method for gradient treatment of metal ions in heavy metal sludge by using deep-sea microorganisms, which comprises the following steps:
1) pumping the sludge into a sludge conditioning tank, adding bacterial liquid with a certain volume ratio, stirring by a stirring device, pumping into a filter tank by a sludge lifting pump, carrying out vacuum filtration by a vacuum pump, carrying out subsequent treatment on a filter cake, and feeding the filtrate into a reservoir;
2) setting more than two microbial catalytic reactors, pumping the filtrate from the reservoir into a first-stage microbial catalytic reactor, treating the filtrate by using a stepwise microbial catalytic reactor, and allowing the wastewater to flow to a circulating pool from a last-stage microbial reactor; wherein,
reducing metal ions in the wastewater into metal ion compound precipitates and/or metal simple substances by reducing metal microorganisms on the biological carriers, periodically supplementing the microorganisms, and periodically replacing the biological carriers and the precipitation tank to recover metals;
or,
and arranging a microbial catalytic reactor, pumping the filtrate into the microbial catalytic reactor from a reservoir, treating the filtrate by the microbial catalytic reactor, directly adsorbing metal ions in the wastewater by microbes on a biological carrier or forming metal ion compound precipitates and/or metal simple substances by utilizing substances generated by a carbon source and the metal ions, periodically supplementing the microbes, periodically replacing the biological carrier and a precipitation tank to recover metals, and allowing the treated wastewater to flow to a circulation tank through a water outlet of the microbial catalytic reactor.
The method according to the present invention, wherein, as an option, step 2) is performed3 microbial catalytic reactors are arranged from top to bottom; the sludge contains Cu2+、Zn2+And Cr6+；
2-1) pumping the filtrate from the reservoir into a first-stage microbial catalytic reactor, and treating the filtrate by the first-stage microbial catalytic reactor to obtain Cu in the wastewater2+Cu on biological Carrier2+Reduction of reducing organisms to Cu+Adding bacteria liquid to compound sediment and Cu simple substance regularly, replacing biological carrier and sediment tank regularly to recover Cu, and making the waste water flow to the second-stage microbial catalytic reactor automatically through the water outlet of the first-stage microbial catalytic reactor;
2-2) the wastewater enters the secondary microbial catalytic reactor from the water inlet of the secondary microbial catalytic reactor, and Zn in the wastewater is treated by the secondary microbial catalytic reactor2+Zn supported by biological carrier2+Reducing the reducing microorganism directly into a Zn simple substance, supplementing bacterial liquid regularly, replacing a biological carrier regularly and a settling tank regularly to recover metal Zn, and automatically flowing the wastewater to a third-stage microbial catalytic reactor through a water outlet of the second-stage microbial catalytic reactor;
2-3) the wastewater enters the three-stage microbial catalytic reactor from the water inlet of the three-stage microbial catalytic reactor, and Cr in the wastewater is treated by the three-stage microbial catalytic reactor6+Cr on biological carrier6+Reducing the direct adsorption of reducing microorganism into Cr3+Precipitating the compound, periodically supplementing bacterial liquid, periodically replacing a biological carrier and a precipitation tank to recover metal Cr, and automatically flowing the wastewater to a third-stage microbial catalytic reactor through a water outlet of the second-stage microbial catalytic reactor;
wherein, the steps 2-1), 2-2) and 2-3) can be interchanged in any order;
2-4) enriching the metal ion Cu by three microbial catalytic reactors2+、Zn2+、Cr6+The waste water is discharged from a water outlet of the three-stage microbial catalytic reactor and automatically flows into a circulating pool.
The method according to the invention, wherein as an option the conditioning tank: temperature range: 15-30 ℃; pH: neutral environment, 5-8; 0.5-2mg/L of dissolved oxygen. Microbial catalytic reactor: temperature range: 15-30 ℃; pH: neutral environment, 5-8; 0.5-1mg/L of dissolved oxygen.
The method according to the invention, wherein the conditioning tank is used for treating the sludge for 3-5 days as an option.
According to the method, as an option, the ratio of the sludge amount in the conditioning tank to the volume of the bacterial liquid is as follows: 11:1-5:1.
According to the method, the volume ratio of the wastewater to the bacterial liquid in the microbial catalytic reactor is 20:1-5: 1.
The bacteria liquid in each reactor (the conditioning tank and the microbial catalytic reactor) is the bacteria liquid with bacteria in the logarithmic phase, the specific concentration of the bacteria liquid is not particularly limited, and the bacteria liquid can be prepared as long as the bacteria in the bacteria liquid are in the logarithmic phase.
According to the method provided by the invention, as an option, the biological carrier in the microbial catalytic reactor is graphite felt and is fixed in the reactor, so that the immobilization of the microorganisms is realized.
The method according to the invention, wherein the flow of wastewater between the microbial catalytic reactors is optionally free-flowing without mechanical transmission.
According to the method of the present invention, preferably, deep-sea microorganisms in each of the microorganism reactors react with only a specific metal ion under specific conditions, and the metal ions are gradient-enriched.
The present invention may treat any heavy metal-containing sludge commonly found in the art, for example, including but not limited to,
municipal sludge (municipal sludge): the sludge produced by the municipal refuse has low heavy metal content.
Metallurgical steel sludge: the sludge mainly produced by smelting steel and nonferrous metals has high heavy metal content and is difficult to treat.
Electroplating sludge: the components of the sludge generated in the electroplating sludge are complex.
Chemical sludge: microbial residues and some refractory substances generated in the sewage treatment process.
The bacterial liquid used in the invention contains various functional strains with the characteristics of heavy metal tolerance, hypoxia and wide temperature application range, and is a composite application of the various functional strains.
Preferably, the bacterial sieve with the characteristics of heavy metal tolerance, hypoxia and wide temperature adaptation range in the bacterial liquid is selected from sediments in a western pacific deep position of 5812 meters in hydrothermal jet and a eastern pacific ocean deep position of 2891 meters in water, and the microorganisms used for treating the sludge and the sludge wastewater are a plurality of composite bacterial strains (original bacterial liquid) screened from the sediments. The strain screening conditions are as follows: the temperature is 0-80 ℃, the pH is 6-7.5, the salt concentration is 3% -17%, and the dissolved oxygen is 0.1-1 mg/L. The invention does not separate and identify the strains, and only utilizes the screening conditions to screen out the original bacterial liquid containing a plurality of strains from the known sediments.
Further, according to the treatment requirements in the conditioning tank and the plurality of microbial reactors, the original bacteria liquid is further subjected to screening treatment by controlling screening conditions, so that the bacteria liquid containing the composite strains, which can be used for the conditioning tank and the plurality of microbial reactors, is obtained.
Preferably, the selected raw bacterial liquid is used as the bacterial liquid in the conditioning tank. And the bacterial liquids in different microbial reactors need to be further screened according to the actual condition of wastewater to be treated.
For example, treating Cu2+And then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 20-30 ℃, the pH is 6-7.5, the salt concentration is 3% -17%, and the dissolved oxygen is 0.1-1 mg/L;
adding CuSO4·5H2O, making Cu in the culture medium2+The content is 10-20 mg/L.
Treatment of Zn2+And then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 20-30 ℃, the pH is 6-7.5, the salt concentration is 3% -17%, and the dissolved oxygen is 0.1-1 mg/L;
adding Zn (NO)3)2·6H2O, making Zn in the culture medium2+The content is 10-20 mg/L.
Treatment of Cr6+Then, it is right toFurther screening strains in the original bacterial liquid, wherein the screening strain conditions are as follows: the temperature is 20-40 ℃, the pH is 6-7.5, the salt concentration is 3% -17%, and the dissolved oxygen is 0.1-1 mg/L;
adding K2Cr2O7Making Cr in the culture medium6+The content is 5-20 mmol/L.
When treating other ions, the principle and treatment of the above Cu2+、Zn2+、Cr6+And similarly, performing corresponding screening treatment on the original bacteria liquid according to the actual condition of the ion reaction to be treated.
The invention belongs to the field of environmental protection-resource comprehensive treatment, and relates to a system and a method for gradient treatment of metal ions in heavy metal sludge by using deep-sea microorganisms2+Directly adsorbed by microorganism on a biological carrier or formed by substances generated by utilizing a carbon source and heavy metal ions+Compound precipitation and Cu simple substance, wastewater automatically flows to a secondary microbial catalytic reactor through a water outlet of the primary microbial catalytic reactor, and Zn in the wastewater2+Is directly adsorbed by microorganism on a biological carrier or is reduced into a Zn simple substance, the wastewater automatically flows to a third-stage microbial catalytic reactor through a water outlet of the second-stage microbial catalytic reactor, and Cr in the wastewater6+Is directly adsorbed or reduced into Cr by microorganisms on the biological carrier3+And (3) precipitating a compound, enriching metal ions Cu, Zn and Cr in the wastewater through three microbial catalytic reactors, pumping the wastewater in the circulating tank into a first-stage microbial catalytic reactor, and performing circulating treatment until the metal content in the circulating tank reaches the standard, and then discharging the wastewater. According to the characteristic that marine microorganisms have uniqueness on metal enrichment, the invention has the advantages that the metal ions in the wastewater are enriched in a gradient manner: has the advantages of no corrosion, environmental protection, good stability, low energy consumption and great purification of wastewater.
Drawings
FIG. 1 is a technical route diagram of the method for gradient treatment of metal ions in heavy metal sludge by deep-sea microorganisms according to the present invention;
FIG. 2 is a structural diagram of an apparatus for gradient treatment of metal ions in heavy metal sludge by deep-sea microorganisms according to the present invention;
reference numerals: 1. a conditioning tank; 2. a stirring device; 3. a sludge lift pump; 4. a vacuum pump; 5. a suction filtration tank; 6. a reservoir; 7. a water pump; 8. a circulation pump; 9. a first stage microbial catalytic reactor; 9-1, a water inlet; 9-2, biological carrier; 9-3, a water outlet; 9-4, a control valve; 9-5, a precipitation tank; 10. a secondary microbial catalytic reactor; 11. a three-stage microbial catalytic reactor; 12. a circulation tank; 13. and a three-way valve.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The invention is described in further detail below with reference to the figures and the detailed description.
Example 1
As shown in fig. 2, a deep sea microorganism gradient system for treating metal ions in heavy metal sludge comprises: the device comprises a conditioning tank 1, a stirring device 2, a sludge lifting pump 3, a vacuum pump 4, a suction filter tank 5, a water storage tank 6, a circulating pump 7, a circulating pump 8, a primary microbial catalytic reactor 9, a water inlet 9-1, a biological carrier 9-2, a water outlet 9-3, a control valve 9-4, a settling tank 9-5, a secondary microbial catalytic reactor 10, a tertiary microbial catalytic reactor 11, a circulating tank 12 and a three-way valve 13;
mud is linked to each other with the 1 mud inlet of conditioning jar by the mud elevator pump, and agitating unit 2 is put in conditioning jar 1, and conditioning jar mud outlet links to each other with 3 one end of mud elevator pump, and other end export links to each other with filter-tank 5, and vacuum pump 4 connects and constitutes vacuum filtration system in the filter-tank bottom, and filter-tank bottom delivery port links to each other with cistern 6.
The 3 microbial catalytic reactors are connected in series from top to bottom for use, a water outlet 9-4 of the first-stage microbial catalytic reactor 9 is connected with a water inlet 9-1 of the second-stage microbial catalytic reactor 9, a water outlet 9-4 of the second-stage microbial catalytic reactor is connected with a water inlet 11-1 of the third-stage microbial catalytic reactor 11, and a water outlet 11-4 of the third-stage microbial catalytic reactor is connected with the buffer tank. The sedimentation tank 9-5 is positioned at the outer side of the bottom of the microbial catalytic reactor and is arranged opposite to the bottom of the biological carrier. 3 microbial catalysis reactors are placed to have a difference in height, and metallurgical waste water flows automatically.
The water pump 7 connects the reservoir with the water inlet of the first-stage microbial catalytic reactor and simultaneously feeds water. The circulating pump 8 connects the circulating pool 12 with the other water inlets of the first-stage microbial catalytic reactor 9, the second-stage microbial catalytic reactor 10 and the third-stage microbial catalytic reactor 11 in parallel through the three-way valve 13, the concentration of each metal ion in the sludge leachate in the circulating pool reaches the discharge standard, and the metal ions are discharged from the water outlet of the circulating pool. If the metal ions do not reach the standard, pumping the metal ions into corresponding microbial catalytic reactors by a circulating pump, sequentially entering each reactor, and then reducing and precipitating each metal until the metal ions reach the discharge standard.
The volume of the conditioning tank is 20-30m3The height between the bottom of the stirring slurry and the bottom of the conditioning tank is 50-90 cm. Height difference exists among the 3 microbial catalytic reactors, the height difference is 100-200cm, and liquid flows automatically.
Example 2
As shown in fig. 1, a method for gradient treatment of metal ions in heavy metal sludge based on the deep-sea microorganisms of example 1 comprises the following steps:
1) the sludge is pumped into the sludge conditioning tank 1 and then added with bacteria liquid with a certain volume ratio, after being stirred by the stirring device 2, the sludge is pumped into the filter tank 5 by the sludge lifting pump 3, the vacuum pump 4 carries out vacuum filtration, the filter cake is subsequently treated, and the filtrate enters the reservoir 6.
2) Pumping the wastewater from the reservoir into a first-stage microbial catalytic reactor, and treating the wastewater by the first-stage microbial catalytic reactor to obtain Cu in the wastewater2+Microorganisms on biological carrier 9-2Directly adsorbing or utilizing substances generated by carbon source and heavy metal ions to form Cu+And (3) adding bacteria liquid to the compound precipitate and the Cu simple substance regularly, replacing the biological carrier and the precipitation tank 9-5 regularly to recover metal Cu, and allowing the wastewater to automatically flow to the secondary microbial catalytic reactor through a water outlet 9-4 of the primary microbial catalytic reactor.
3) The wastewater enters the secondary microbial catalytic reactor from the water inlet of the secondary microbial catalytic reactor and is treated by the secondary microbial catalytic reactor, and Zn in the wastewater2+Directly adsorbed by microbes on the biological carrier or reduced into a Zn simple substance, periodically supplemented with bacterial liquid, periodically replaced with the biological carrier and a precipitation tank to recover metal Zn, and the wastewater automatically flows to a third-stage microbial catalytic reactor through a water outlet of the second-stage microbial catalytic reactor.
4) The wastewater enters the three-stage microbial catalytic reactor from the water inlet of the three-stage microbial catalytic reactor and is treated by the three-stage microbial catalytic reactor, and then Cr in the wastewater6+Is directly adsorbed or reduced into Cr by microorganisms on the biological carrier3+And (3) precipitating the compound, periodically supplementing bacterial liquid, periodically replacing the biological carrier and the precipitation tank to recover metal Cr, and automatically flowing the wastewater to the third-stage microbial catalytic reactor through a water outlet of the second-stage microbial catalytic reactor.
5) After the three microbial catalytic reactors enrich the metal ions Cu, Zn and Cr, the wastewater is discharged from a water outlet 11-4 of the three-stage microbial catalytic reactor and automatically flows into a circulating pool, a circulating pump 8 connects the circulating pool 12 with a first-stage microbial catalytic reactor 9, a second-stage microbial catalytic reactor 10 and a three-stage microbial catalytic water inlet, and the concentration of each metal ion in sludge leachate in the circulating pool reaches the discharge standard and is discharged from a water outlet of the circulating pool. If the metal ions do not reach the standard, pumping the metal ions into corresponding microbial catalytic reactors by a circulating pump, sequentially entering each reactor, and then reducing and precipitating each metal until the metal ions reach the discharge standard.
In the step 1), the sludge treatment time of the conditioning tank is 3-5 days; the sludge amount and the bacteria liquid volume in the conditioning tank are as follows: 11:1-5:1.
In the step 1)2)3), the volume ratio of the wastewater in the microbial catalytic reactor to the bacterial liquid is 20:1-5: 1.
The bacterial sieve with the characteristics of heavy metal tolerance, hypoxia and wide temperature application range in the bacterial liquid is selected from sediments with the depth of a western Pacific ocean of 5812 meters and the depth of a Topacific ocean of 2891 meters, and microorganisms used for treating sludge and sludge wastewater in the invention are a plurality of composite bacterial strains (original bacterial liquid) screened from the sediments. The strain screening conditions are as follows: the temperature is 0-80 ℃, the pH is 6-7.5, the salt concentration is 3% -17%, and the dissolved oxygen is 0.1-1 mg/L.
The selected original bacterial liquid is used as the bacterial liquid in the conditioning tank.
Treating Cu2+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 20-30 ℃, the pH is 6-7.5, the salt concentration is 3% -17%, and the dissolved oxygen is 0.1-1 mg/L; adding CuSO4·5H2O, making Cu in the culture medium2+The content is 10-20 mg/L.
Treatment of Zn2+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 20-30 ℃, the pH is 6-7.5, the salt concentration is 3% -17%, and the dissolved oxygen is 0.1-1 mg/L; adding Zn (NO)3)2·6H2O, making Zn in the culture medium2+The content is 10-20 mg/L.
Treatment of Cr6+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 20-40 ℃, the pH is 6-7.5, the salt concentration is 3% -17%, and the dissolved oxygen is 0.1-1 mg/L; adding K2Cr2O7Making Cr in the culture medium6+The content is 5-20 mmol/L.
In the step 1)2)3), the biological carrier in the microbial catalytic reactor is graphite felt and is fixed in the reactor to realize immobilization of microorganisms, and the graphite felt and the precipitation tank are periodically replaced to recover metals.
In the step 1)2)3), the deep-sea microorganisms in each microbial reactor only react with a specific metal ion under specific conditions, and the metal ions are enriched in a gradient manner.
In the steps, 3 microbial catalytic reactors are in self-flow without mechanical transmission.
Example 3
The chemical multi-element analysis of municipal sludge taken from a certain area of Beijing is as follows: municipal sludge from some area of Beijing was subjected to the chemical multielement analysis as follows:
the municipal sludge has high water content, pH of 6.59 and water content of 90 percent, and is rich in N, P, K and heavy metals such as Cd, Cr, Cu, Pb, Zn and the like.
System according to example 1 and method according to example 2, wherein the conditioning tank has a volume of 20m3The height between the bottom of the stirring slurry and the bottom of the conditioning tank is 50 cm. The height difference among the 3 microbial catalytic reactors is 100cm, and the liquid flows automatically; the sludge amount and the bacteria liquid ratio in the conditioning tank are as follows: 11:1. Pumping a certain amount of sludge into a conditioning tank, adding 11% of marine microorganisms, stirring for 3d by a stirring device, pumping the conditioned sludge into a filter tank, carrying out suction filtration by a vacuum pump, carrying out suction filtration to obtain a filter cake, bagging, and automatically flowing the filtrate into a reservoir. Pumping the wastewater from the reservoir into a first-stage microbial catalytic reactor, and adsorbing and reducing marine microorganisms attached to a graphite felt with Cu ions in the wastewater to obtain a Cu simple substance and Cu+Precipitating the compound, periodically replacing a graphite felt and a precipitation tank, and recovering Cu. The wastewater automatically flows into a secondary microbial catalytic reactor, marine microorganisms are attached to a graphite felt to react with Zn ions in the wastewater to obtain a Zn simple substance, the graphite felt and a settling tank are periodically replaced, and Zn is recovered. The wastewater automatically flows into a secondary microorganism catalytic reactor, and marine microorganisms are attached to a graphite felt to react with Cr ions in the wastewater to obtain Cr3+The graphite felt and the precipitation tank are periodically replaced to recover Cr. And finally, automatically flowing the wastewater into a circulating tank, and performing circulating treatment until the metal content in the circulating tank reaches the standard and then discharging the wastewater. In each microbial catalytic reactor, the volume ratio of the wastewater to the bacterial liquid is 20: 1.
The bacterial sieve with the characteristics of heavy metal tolerance, hypoxia and wide temperature application range in the bacterial liquid is selected from sediments with the depth of a western Pacific ocean of 5812 meters and the depth of a Topacific ocean of 2891 meters, and microorganisms used for treating sludge and sludge wastewater in the invention are a plurality of composite bacterial strains (original bacterial liquid) screened from the sediments. The strain screening conditions are as follows: the temperature was 40 ℃, pH7.0, salt concentration 10%, dissolved oxygen 0.5 mg/L.
The selected original bacterial liquid is used as the bacterial liquid in the conditioning tank.
Treating Cu2+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 25 ℃, the pH value is 7.0, the salt concentration is 10 percent, and the dissolved oxygen is 0.5 mg/L; adding CuSO4·5H2O, making Cu in the culture medium2+The content was 15 mg/L.
Treatment of Zn2+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 25 ℃, the pH value is 7.0, the salt concentration is 10 percent, and the dissolved oxygen is 0.5 mg/L; adding Zn (NO)3)2·6H2O, making Zn in the culture medium2+The content was 15 mg/L.
Treatment of Cr6+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 30 ℃, the pH value is 7.0, the salt concentration is 15 percent, and the dissolved oxygen is 0.5 mg/L; adding K2Cr2O7Making Cr in the culture medium6+The content was 15 mmol/L.
According to the experiment, the COD in the filtrate is low, the organic matter is fully decomposed, the organic matter content in the finally obtained filter cake is 30%, and the water content is 20%; the Zn content in the water without heavy metals is 3.2mg/L, the Cu content is 2.1mg/L, the Pb content is 0.9mg/L, the Cr content is 1.1mg/L, the heavy metals content in the water is lower than the national standard, and the obtained heavy metals can be recycled.
Example 4
The chemical multi-element analysis of the mixed sludge of metallurgical steel taken from a certain area is as follows:
system according to example 1 and method according to example 2, wherein the conditioning tank has a volume of 30m3The bottom of the stirring paddle andthe height of the bottom of the conditioning tank is 90 cm. The height difference among the 3 microbial catalytic reactors is 200cm, and the liquid flows automatically; the sludge amount in the conditioning tank and the volume ratio of the bacteria liquid are as follows: 5:1. Pumping a certain amount of sludge into a conditioning tank, adding 20% of marine microorganisms, stirring for 5 days by a stirring device, pumping the conditioned sludge into a filter tank, carrying out suction filtration by a vacuum pump, carrying out suction filtration to obtain a filter cake, bagging, and automatically flowing the filtrate into a reservoir. Pumping the wastewater from the reservoir into a first-stage microbial catalytic reactor, and adsorbing and reducing marine microorganisms attached to a graphite felt with Cu ions in the wastewater to obtain a Cu simple substance and Cu+Precipitating the compound, periodically replacing a graphite felt and a precipitation tank, and recovering Cu. The wastewater automatically flows into a secondary microbial catalytic reactor, marine microorganisms are attached to a graphite felt to react with Zn ions in the wastewater to obtain a Zn simple substance, the graphite felt and a settling tank are periodically replaced, and Zn is recovered. The wastewater automatically flows into a secondary microorganism catalytic reactor, and marine microorganisms are attached to a graphite felt to react with Cr ions in the wastewater to obtain Cr3+The graphite felt and the precipitation tank are periodically replaced to recover Cr. And finally, automatically flowing the wastewater into a circulating tank, and performing circulating treatment until the metal content in the circulating tank reaches the standard and then discharging the wastewater. In each microbial catalytic reactor, the volume ratio of the wastewater to the bacterial liquid is 5: 1.
The bacterial sieve with the characteristics of heavy metal tolerance, hypoxia and wide temperature application range in the bacterial liquid is selected from sediments with the depth of a western Pacific ocean of 5812 meters and the depth of a Topacific ocean of 2891 meters, and microorganisms used for treating sludge and sludge wastewater in the invention are a plurality of composite bacterial strains (original bacterial liquid) screened from the sediments. The strain screening conditions are as follows: the temperature was 0 ℃, pH6.0, salt concentration 3%, dissolved oxygen 0.1 mg/L.
The selected original bacterial liquid is used as the bacterial liquid in the conditioning tank.
Treating Cu2+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 20 ℃, the pH value is 6.0, the salt concentration is 3 percent, and the dissolved oxygen is 0.1 mg/L; adding CuSO4·5H2O, making Cu in the culture medium2+The content is 10 mg/L.
Treatment of Zn2+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 20 ℃, the pH value is 6.0, the salt concentration is 3 percent, and the dissolved oxygen is 0.1 mg/L; adding Zn (NO)3)2·6H2O, making Zn in the culture medium2+The content is 10 mg/L.
Treatment of Cr6+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 20 ℃, the pH value is 6.0, the salt concentration is 3 percent, and the dissolved oxygen is 0.1 mg/L; adding K2Cr2O7Making Cr in the culture medium6+The content was 5 mmol/L.
According to the experiment, the COD in the filtrate is low, the organic matter is fully decomposed, the organic matter content in the finally obtained filter cake is 30%, and the water content is 20%; the Zn content in the water without heavy metals is 3.5mg/L, the Cu content is 2.5mg/L, the Pb content is 1.2mg/L, the Cr content is 1.2mg/L, the heavy metals content in the water is lower than the national standard, and the obtained heavy metals can be recycled.
Example 5
The chemical multi-element analysis of electroplating sludge taken from a certain area is as follows:
the selected industrial sludge is electroplating sludge with pH 7.99, water content 90%, low Cd and Pb content, Zn, Cu and Cr content higher than the national standard value, and low content of N, P, K, S and other nutritive elements.
System according to example 1 and method according to example 2, wherein the conditioning tank has a volume of 25m3The height between the bottom of the stirring slurry and the bottom of the conditioning tank is 70 cm. The height difference among the 3 microbial catalytic reactors is 150cm, and the liquid flows automatically; the proportion of the sludge amount in the conditioning tank to the bacteria adding amount is as follows: 8:1. Pumping a certain amount of sludge into a conditioning tank, adding 15% of marine microorganisms, stirring for 5 days by a stirring device, pumping the conditioned sludge into a filter tank, carrying out suction filtration by a vacuum pump, carrying out suction filtration to obtain a filter cake, bagging, and automatically flowing the filtrate into a reservoir. Pumping the waste water from the water storage tank into a first-stage microbial catalytic reactor, and attaching marine microorganisms to the waste waterCarrying out adsorption and reduction reaction on the graphite felt and Cu ions in the wastewater to obtain a Cu simple substance and Cu+Precipitating the compound, periodically replacing the graphite felt, and recovering Cu. The wastewater automatically flows into a secondary microbial catalytic reactor, marine microorganisms are attached to a graphite felt to react with Zn ions in the wastewater to obtain a Zn simple substance, the graphite felt and a settling tank are periodically replaced, and Zn is recovered. The wastewater automatically flows into a secondary microorganism catalytic reactor, and marine microorganisms are attached to a graphite felt to react with Cr ions in the wastewater to obtain Cr3+The graphite felt and the precipitation tank are periodically replaced to recover Cr. And finally, automatically flowing the wastewater into a circulating tank, and performing circulating treatment until the metal content in the circulating tank reaches the standard and then discharging the wastewater. In each microbial catalytic reactor, the volume ratio of the wastewater to the bacterial liquid is 10: 1.
The bacterial sieve with the characteristics of heavy metal tolerance, hypoxia and wide temperature application range in the bacterial liquid is selected from sediments with the depth of a western Pacific ocean of 5812 meters and the depth of a Topacific ocean of 2891 meters, and microorganisms used for treating sludge and sludge wastewater in the invention are a plurality of composite bacterial strains (original bacterial liquid) screened from the sediments. The strain screening conditions are as follows: the temperature was 80 ℃, pH7.5, salt concentration was 17%, and dissolved oxygen was 1 mg/L.
The selected original bacterial liquid is used as the bacterial liquid in the conditioning tank.
Treating Cu2+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 30 ℃, the pH value is 7.5, the salt concentration is 17 percent, and the dissolved oxygen is 1 mg/L; adding CuSO4·5H2O, making Cu in the culture medium2+The content is 20 mg/L.
Treatment of Zn2+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 30 ℃, the pH value is 7.5, the salt concentration is 17 percent, and the dissolved oxygen is 1 mg/L; adding Zn (NO)3)2·6H2O, making Zn in the culture medium2+The content is 20 mg/L.
Treatment of Cr6+Then, further screening the strains in the original bacterial liquid, wherein the conditions for screening the strains are as follows: the temperature is 40 ℃, the pH value is 7.5, the salt concentration is 17 percent, and the dissolved oxygen is 1 mg/L; adding K2Cr2O7To makeCr in the culture Medium6+The content was 20 mmol/L.
According to the experiment, the COD in the filtrate is low, the organic matter is fully decomposed, the organic matter content in the finally obtained filter cake is 30%, and the water content is 20%; the Zn content in the water without heavy metals is 3.4mg/L, the Cu content is 2.2mg/L, the Pb content is 0.9mg/L, the Cr content is 1.2mg/L, the heavy metals content in the water is lower than the national standard, and the obtained heavy metals can be recycled.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. An apparatus for gradient treatment of metal ions in heavy metal sludge by deep sea microorganisms, the apparatus comprising: a heavy metal leaching system and a heavy metal reduction enrichment system;
the heavy metal leaching system comprises a sludge conditioning tank, a stirring device, a sludge lifting pump, a vacuum pump and a filter tank;
a stirring head of the stirring device is arranged in a conditioning tank, a sludge outlet of the conditioning tank is connected with a feed inlet of a sludge lifting pump, a discharge outlet of the sludge lifting pump is connected with a filter tank, a vacuum pump is connected to the outer side of the bottom of the filter tank to form a vacuum filtration system, and a water outlet at the bottom of the filter tank is connected with a reservoir;
the heavy metal reduction and enrichment system consists of one or more than two microbial catalytic reactors, a circulating pool, a water pump, a circulating pump and a reservoir;
the microbial catalytic reactor comprises a water inlet, a biological carrier and a water outlet; the biological carrier is arranged inside the microbial catalytic reactor; wherein,
when more than two microbial catalytic reactors are arranged, the microbial catalytic reactors are connected in series from top to bottom, the water outlet of the upper-stage microbial catalytic reactor is connected with the water inlet of the next-stage microbial catalytic reactor, and the water outlet of the last-stage microbial catalytic reactor is connected with the circulating pool;
the water pump connects the reservoir with the water inlet of the first-stage microbial catalytic reactor, and the circulating pump connects the circulating tank with the other water inlet of each stage of microbial catalytic reactor in parallel;
or,
when the microbial catalytic reactor is one, the water outlet of the microbial catalytic reactor is connected with the circulating pool, the water reservoir is connected with the water inlet of the microbial catalytic reactor by the water pump, and the circulating pool is connected with the water inlet of the microbial catalytic reactor by the circulating pump.
2. The apparatus of claim 1, wherein the conditioning tank has a volume of 20-30m3The height between the bottom of the stirring head and the bottom of the conditioning tank is 50-90 cm.
3. The apparatus as claimed in claim 1, wherein when the number of the microbial catalytic reactors is two or more, the height difference between the microbial catalytic reactors of each stage is 100-200 cm.
4. A method for gradient treatment of metal ions in heavy metal sludge by deep sea microorganisms comprises the following steps:
1) pumping the sludge into a sludge conditioning tank, adding bacterial liquid with a certain volume ratio, stirring by a stirring device, pumping into a filter tank by a sludge lifting pump, carrying out vacuum filtration by a vacuum pump, carrying out subsequent treatment on a filter cake, and feeding the filtrate into a reservoir;
2) setting more than two microbial catalytic reactors, pumping the filtrate from the reservoir into a first-stage microbial catalytic reactor, treating the filtrate by using a stepwise microbial catalytic reactor, and allowing the wastewater to flow to a circulating pool from a last-stage microbial reactor; wherein, the metal ions in the wastewater are reduced into metal ion compound precipitates and/or metal simple substances by reducing metal microorganisms on the biological carriers, the microorganisms are supplemented periodically, and the biological carriers and the precipitation tank are replaced periodically to recover metals;
or,
and arranging a microbial catalytic reactor, pumping the filtrate from the water reservoir to the microbial catalytic reactor, treating by the microbial catalytic reactor, reducing metal ions in the wastewater into metal ion compound precipitates and/or metal simple substances by microorganisms on a biological carrier, periodically supplementing the microorganisms, periodically replacing the biological carrier and a precipitation tank to recover metals, and allowing the treated wastewater to flow to a circulating tank through a water outlet of the microbial catalytic reactor.
5. The method of claim 4, wherein 3 of the microbial catalytic reactors of step 2) are arranged from top to bottom; the sludge contains Cu2+、Zn2+And Cr6+；
2-1) pumping the filtrate from the reservoir into a first-stage microbial catalytic reactor, and treating the filtrate by the first-stage microbial catalytic reactor to obtain Cu in the wastewater2+Cu on biological Carrier2+Reduction of reducing organisms to Cu+Precipitating a compound and a Cu simple substance, and automatically flowing the wastewater to a secondary microbial catalytic reactor through a water outlet of the primary microbial catalytic reactor;
2-2) the wastewater enters the secondary microbial catalytic reactor from the water inlet of the secondary microbial catalytic reactor, and Zn in the wastewater is treated by the secondary microbial catalytic reactor2+Zn supported by biological carrier2+Reducing the reducing microorganism into a Zn simple substance, and automatically flowing the wastewater to a third-stage microbial catalytic reactor through a water outlet of the second-stage microbial catalytic reactor;
2-3) the wastewater enters the three-stage microbial catalytic reactor from the water inlet of the three-stage microbial catalytic reactor, and Cr in the wastewater is treated by the three-stage microbial catalytic reactor6+Cr on biological carrier6+Reduction of reducing organisms to Cr3+Precipitating a compound, wherein the wastewater automatically flows to a third-stage microbial catalytic reactor through a water outlet of the second-stage microbial catalytic reactor;
wherein, the steps 2-1), 2-2) and 2-3) can be interchanged in any order;
2-4) enriching the metal ion Cu by three microbial catalytic reactors2+、Zn2+、Cr6+The waste water is discharged from a water outlet of the three-stage microbial catalytic reactor and automatically flows into a circulating pool.
6. The method of claim 4 or 5, wherein the conditioning tank treats the sludge for 3-5 days.
7. The method according to claim 4 or 5, wherein the ratio of the sludge amount in the conditioning tank to the bacteria liquid volume is: 11:1-5: 1; the volume ratio of the waste water to the bacterial liquid in the microbial catalytic reactor is 20:1-5: 1.
8. The method as claimed in claim 4 or 5, wherein the biological carrier in the microbial catalytic reactor is graphite felt and is fixed in the reactor to realize the immobilization of the microorganisms.
9. The method of claim 4 or 5, wherein the flow of wastewater between the microbial catalytic reactors is free-flowing without mechanical transmission.
10. The method according to claim 4 or 5, characterized in that the conditioning tank: temperature: 15-30 ℃; pH: 5-8; 0.5-2mg/L of dissolved oxygen;
microbial catalytic reactor: temperature: 15-30 ℃; pH: 5-8; 0.5-1mg/L of dissolved oxygen.
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