CN114163086A - Treatment device and method for heavy metal polluted wastewater - Google Patents

Treatment device and method for heavy metal polluted wastewater Download PDF

Info

Publication number
CN114163086A
CN114163086A CN202111574776.0A CN202111574776A CN114163086A CN 114163086 A CN114163086 A CN 114163086A CN 202111574776 A CN202111574776 A CN 202111574776A CN 114163086 A CN114163086 A CN 114163086A
Authority
CN
China
Prior art keywords
heavy metal
green algae
electrophoresis chamber
solution
photobioreactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111574776.0A
Other languages
Chinese (zh)
Other versions
CN114163086B (en
Inventor
路延笃
费亚兹·艾赫迈德
瑙润·艾斯茹弗
崔鑫宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hainan University
Original Assignee
Hainan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hainan University filed Critical Hainan University
Priority to CN202111574776.0A priority Critical patent/CN114163086B/en
Priority to PCT/CN2021/141907 priority patent/WO2023115607A1/en
Publication of CN114163086A publication Critical patent/CN114163086A/en
Application granted granted Critical
Publication of CN114163086B publication Critical patent/CN114163086B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4696—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrophoresis
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • 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
    • C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
    • C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention relates to the technical field of wastewater treatment and heavy metal recovery, in particular to a device and a method for treating heavy metal polluted wastewater. In the second photobioreactor, microalgae and extracellular secretion thereof interact with heavy metal ions to reduce the heavy metal ions into zero-valent heavy metal particles, and the zero-valent heavy metal particles can be attached to the surface of cells or penetrate cell membranes to reach the cytoplasmic parts of the cells to finally form precipitates. The heavy metal nanoparticles formed by the action of extracellular secretions can be enriched and removed from the water body through electrophoresis. And (3) the water discharged from the electrophoresis chamber enters a first sedimentation tank, sedimentation is carried out in the first sedimentation tank, the obtained supernatant is the treated water, and the removal rate of heavy metal ions in the treated water is higher through detection. Meanwhile, the sediments at the bottom of the electrophoresis chamber and the bottom of the first sedimentation tank are collected, and heavy metals can be recovered.

Description

Treatment device and method for heavy metal polluted wastewater
Technical Field
The invention relates to the technical field of wastewater treatment and heavy metal recovery, in particular to a device and a method for treating heavy metal polluted wastewater.
Background
With the advance of industrialization, the demand of human beings for heavy metals is increasing. Mining and heavy metal-containing industrial waste water is also being produced at an increasing rate. In these processes, heavy metals in the wastewater are released directly or indirectly into the surrounding water body, entering rivers and the sea. Heavy metal contamination poses serious threats to the health of living beings. The environment is increasingly deteriorated due to the high toxicity, non-degradability and accumulation of heavy metals in the food chain and organisms. On the other hand, heavy metals are non-renewable resources. The recovery and reuse of the waste water are of great significance for the development of recycling economy. Meanwhile, the purified water resource can be reused, and the water resource is saved. The conventional treatment method of heavy metal polluted water based on a physical and chemical method usually leads heavy metal to interact with solid particles (organic matters) to form sediment, and finally the sediment is deposited at the bottom of water. In order to realize the reuse of water bodies, circulating water treatment systems including those based on membrane filtration systems, chemical methods, physical methods and biological methods have been developed. Among the methods, the biological method becomes a research hotspot for heavy metal treatment due to the mildness, high efficiency and no secondary pollution. Nevertheless, there is no system/method that can simultaneously remove (purify) and recover heavy metals from polluted water. Therefore, it is necessary to develop a technical device system that can effectively remove heavy metals from polluted water and recycle heavy metals.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a device and a method for treating heavy metal polluted wastewater, wherein the device is used for treating heavy metal polluted wastewater, and the removal rate of heavy metal ions in the treated water body is high.
The invention provides a treatment device for heavy metal polluted wastewater, which comprises:
a reservoir;
a first photobioreactor; a glass tube is arranged in the first photobioreactor; one end of the glass tube is connected with an air pump and is used for providing air for the green algae culture solution in the first photobioreactor;
heavy metal polluted wastewater discharged from a water outlet of the reservoir is mixed with green algae culture solution discharged from a green algae culture solution outlet of the first photobioreactor and then enters a second photobioreactor;
an electrophoresis chamber; an anode and a cathode are arranged in the electrophoresis chamber; the electrophoresis chamber is provided with a water inlet and a water outlet; a sediment outlet is arranged at the bottom of the electrophoresis chamber; the water inlet of the electrophoresis chamber is connected with the water outlet of the second photobioreactor;
the first sedimentation tank is connected with a water outlet of the electrophoresis chamber; the first sedimentation tank is provided with a water outlet; the treated water body is discharged from a water outlet of the first sedimentation tank;
a collection tank provided with a first precipitation inlet; and the first precipitation inlet of the collection tank is connected with the precipitation outlet of the electrophoresis chamber.
Preferably, the processing device further comprises a solar panel and a voltage controller;
the air pump receives required electric energy from the solar panel through the voltage controller;
and the anode and the cathode in the electrophoresis chamber are connected with the voltage controller, and the electrophoresis chamber receives required electric energy from the solar panel through the voltage controller.
Preferably, a stirrer is arranged in the second photobioreactor;
the stirrer is connected with an electric motor; the electric motor receives the required electric power from the solar panel through the voltage controller.
Preferably, the bottom of the electrophoresis chamber is a tapered bottom.
Preferably, the bottom of the first sedimentation tank is a conical bottom.
The invention also provides a method for treating heavy metal polluted wastewater by using the treatment device, which comprises the following steps:
A) mixing the heavy metal polluted wastewater with a green algae culture solution, and culturing under the irradiation of a light source to obtain a treatment solution; the luminous intensity of the light source is 95-105 mu mol m-2s-1；
B) Transferring the treatment fluid to an electrophoresis chamber; applying a voltage of 4-20V between the anode and the cathode, and treating for 18-48 h to obtain a first precipitate and a first supernatant;
C) and transferring the first precipitate to a collection tank, transferring the first supernatant to a first sedimentation tank, and standing for 46-50 h to obtain a second supernatant, namely the treated water body.
Preferably, in the heavy metal polluted wastewater, the concentration of lead ions is 0.01-200 ppm, and the concentration of copper ions is 0.01-120 ppm;
the pH value of the heavy metal polluted wastewater is 5-10.
Preferably, the green algae culture solution is prepared according to the following method:
under the illumination, culturing the green algae in a sterilized liquid culture medium at 25-40 ℃ until the logarithmic phase of the growth of the green algae to obtain a green algae culture solution; the luminous intensity of the illumination is 95-105 mu mol m-2s-1；
The green algae in the green algae culture solution is the green algae with the preservation number of CCTCC No: m20211083 green algae and/or green algae with preservation number of CCTCC No: m20211084 green algae.
Preferably, the liquid medium is prepared according to the following method:
a1) mixing a sea salt solution with tris (hydroxymethyl) aminomethane to obtain a first mixed solution; in the first mixed solution, the concentration of sea salt is 35g/L, and the concentration of tris (hydroxymethyl) aminomethane is 1.21 g/L;
a2) adjusting the pH value of the first mixed solution to 7.5-8, and sterilizing at 120-122 ℃ for 18-22 min to obtain a second mixed solution;
a3) mixing sodium nitrate, sodium dihydrogen phosphate monohydrate and a trace element solution, sterilizing at 120-122 ℃ for 13-17 min, and adding the mixture into the second mixed solution to obtain a third mixed solution; in the second mixed solution, the addition amount of sodium nitrate is 5g/L, the addition amount of sodium dihydrogen phosphate monohydrate is 5g/L, and the addition amount of a trace element solution is 1 g/L;
the trace element solution is prepared by mixing raw materials including copper sulfate pentahydrate, sodium molybdate dihydrate, zinc sulfate heptahydrate, cobalt chloride hexahydrate and manganese chloride tetrahydrate, and sterilizing at 120-122 ℃ for 18-22 min;
in the trace element solution, the concentration of copper sulfate pentahydrate is 19.6g/L, the concentration of sodium molybdate dihydrate is 12.6g/L, the concentration of zinc sulfate heptahydrate is 44.0g/L, the concentration of cobalt chloride hexahydrate is 10.92g/L, and the concentration of manganese chloride tetrahydrate is 360 g/L.
Preferably, in the step A), OD of a mixed solution obtained by mixing the heavy metal contaminated wastewater with the green algae culture solution7500.3 to 0.5;
the culture is carried out under the condition of stirring, and the rotating speed of the stirring is 18-22 rpm;
the culture temperature is 24-35 ℃, and the culture time is 168-192 hours.
The invention provides a treatment device for heavy metal polluted wastewater, which comprises: a reservoir; a first photobioreactor; a glass tube is arranged in the first photobioreactor; one end of the glass tube is connected with an air pump and is used for providing air for the green algae culture solution in the first photobioreactor; heavy metal polluted wastewater discharged from a water outlet of the reservoir is mixed with green algae culture solution discharged from a green algae culture solution outlet of the first photobioreactor and then enters a second photobioreactor; an electrophoresis chamber; an anode and a cathode are arranged in the electrophoresis chamber; the electrophoresis chamber is provided with a water inlet and a water outlet; a sediment outlet is arranged at the bottom of the electrophoresis chamber; the water inlet of the electrophoresis chamber is connected with the water outlet of the second photobioreactor; the first sedimentation tank is connected with a water outlet of the electrophoresis chamber; the first sedimentation tank is provided with a water outlet; the treated water body is discharged from a water outlet of the first sedimentation tank; the collecting tank is provided with a first precipitation inlet and a second precipitation inlet; the first sediment import of collection tank with the sediment export of electrophoresis cavity links to each other, the second of collection tank deposits the import with the sediment export of first sedimentation tank links to each other.
In the second photobioreactor, microalgae and extracellular secretion thereof interact with heavy metal ions to reduce the heavy metal ions into zero-valent heavy metal particles, and the zero-valent heavy metal particles can be attached to the surface of cells or penetrate cell membranes to reach the cytoplasmic parts of the cells to finally form precipitates. The heavy metal nanoparticles formed by the action of extracellular secretions can be enriched and removed from the water body through electrophoresis. And (3) the water discharged from the electrophoresis chamber enters a first sedimentation tank, sedimentation is carried out in the first sedimentation tank, the obtained supernatant is the treated water, and the removal rate of heavy metal ions in the treated water is higher through detection. Meanwhile, the sediments at the bottom of the electrophoresis chamber and the bottom of the first sedimentation tank are collected, and heavy metals can be recovered.
The treatment device provided by the invention can be used for treating and repairing multiple water bodies such as fresh water, seawater, industrial wastewater, urban wastewater and the like, so that the cyclic utilization of water resources is realized. Meanwhile, the recovery of the heavy metal enriched by electrophoresis can be realized. Finally, the obtained mixture of the microalgae and the heavy metal can be used for further recovering the heavy metal by developing biodiesel, so that the resource utilization of the microalgae is realized.
Biological preservation Instructions
The green alga MEM-A-403 is classified and named as: clorella sorokiniana MEM-A-403, deposited at the China center for type culture Collection at 25.08 months in 2021, at the address: china, Wuhan university, the preservation number is CCTCC No: m20211083.
The green alga MEM-A-404 is classified and named as: micrum sp.mem-a-404, deposited at the chinese type culture collection at 25/08/2021, at the address: china, Wuhan university, the preservation number is CCTCC No: m20211084.
Drawings
FIG. 1 is a schematic diagram of an apparatus for treating heavy metal-contaminated wastewater according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a treatment device for heavy metal polluted wastewater, which comprises:
a reservoir;
a first photobioreactor; a glass tube is arranged in the first photobioreactor; one end of the glass tube is connected with an air pump and is used for providing air for the green algae culture solution in the first photobioreactor;
heavy metal polluted wastewater discharged from a water outlet of the reservoir is mixed with green algae culture solution discharged from a green algae culture solution outlet of the first photobioreactor and then enters a second photobioreactor;
an electrophoresis chamber; an anode and a cathode are arranged in the electrophoresis chamber; the electrophoresis chamber is provided with a water inlet and a water outlet; a sediment outlet is arranged at the bottom of the electrophoresis chamber; the water inlet of the electrophoresis chamber is connected with the water outlet of the second photobioreactor;
the first sedimentation tank is connected with a water outlet of the electrophoresis chamber; the first sedimentation tank is provided with a water outlet; the treated water body is discharged from a water outlet of the first sedimentation tank;
the collecting tank is provided with a first precipitation inlet and a second precipitation inlet; the first sediment import of collection tank with the sediment export of electrophoresis cavity links to each other, the second of collection tank deposits the import with the sediment export of first sedimentation tank links to each other.
FIG. 1 is a schematic diagram of an apparatus for treating heavy metal-contaminated wastewater according to an embodiment of the present invention. Wherein, 1 is a reservoir; 2 is a first valve; 3 is a first photobioreactor; 4 is a glass tube; 5. a first conduit; 6 is an air pump; 7 is a first electric wire; 8 is a voltage controller; 9 is a second wire; 10 is a solar cell panel; 11 is a second valve; 12 is a first adjustable chuck; 13 is a second adjustable chuck; 14 is a first support stand; 15 is a second support stand; 16 is a second photobioreactor; 17 is a stirrer; 18 is a third valve; 19 is a third electric wire; 20 is an electric motor; 21 is a fourth valve; 22 is a fifth valve; 23 is an electrophoresis chamber; 24 is an anode; 25 is a cathode; 26 is a fourth electric wire; 27 is the tapered bottom of the electrophoresis chamber; 28 is a second conduit; 29 is a collecting tank; 30 is a sixth valve; 31 is a first sedimentation tank; 32 is a seventh valve; an eighth valve 33; 34 is a ninth valve; 35 is a tenth valve; 36 is a second sedimentation tank; and 37 is an eleventh valve.
The device for treating the heavy metal polluted wastewater comprises a reservoir 1. The reservoir is used for storing heavy metal polluted wastewater. The structure, material and source of the reservoir are not particularly limited in the present invention, and a reservoir known to those skilled in the art may be used, and in some embodiments of the present invention, the reservoir is in the shape of a cylinder with a diameter of 9cm at the bottom and a height of 24 cm.
The reservoir is provided with a water outlet. In some embodiments of the invention, a first valve 2 is provided at the outlet of the reservoir.
The device for treating the heavy metal polluted wastewater further comprises a first photobioreactor 3. The first photobioreactor is used for culturing microalgae, and then a green algae culture solution is prepared.
In the invention, a glass tube 4 is arranged in the first photobioreactor; one end of the glass tube is connected with an air pump 6 and is used for providing air for the green algae culture solution in the first photobioreactor. In certain embodiments of the invention, one end of the glass tube is connected to an air pump 6 via a first conduit 5. In certain embodiments of the present invention, the air pump may be a generally commercially available air pump. In some embodiments of the present invention, the first pipe is made of quartz glass.
The structure and source of the first photobioreactor are not particularly limited, and the first photobioreactor may be a general commercially available photobioreactor.
In some embodiments of the present invention, the first photobioreactor has a second valve 11 at the outlet of the green algae culture solution.
In some embodiments of the invention, the processing means further comprises a solar panel 10 and a voltage controller 8.
In some embodiments of the invention, the air pump receives the required electrical power from the solar panel through a voltage controller. In some embodiments, the air pump and the voltage controller are connected by a first electrical wire 7. In some embodiments, the voltage controller and the solar panel are connected by a second wire 9.
The device for treating the heavy metal polluted wastewater further comprises a second photobioreactor 16. The second photobioreactor is used for treating heavy metal polluted wastewater.
And mixing the heavy metal polluted wastewater discharged from the water outlet of the water storage pool with the green algae culture solution discharged from the green algae culture solution outlet of the first photobioreactor, and then feeding the mixture into a second photobioreactor.
In certain embodiments of the invention, an agitator 17 is provided in the second photobioreactor; the stirrer is connected with an electric motor; the electric motor receives the required electric power from the solar panel through the voltage controller. In some embodiments, the electric motor and the voltage controller are connected by a third wire 19.
The structure and source of the second photobioreactor are not particularly limited in the present invention, and the second photobioreactor may be a general commercially available photobioreactor.
In some embodiments of the invention, a second photobioreactor may be placed on a second support stand 15 to which the electric motor is fixed by means of the first adjustable clamp 12. In some embodiments of the invention, the first photobioreactor may be placed on a first support block 14, which is fixed to a second support block by a second adjustable clamp 13. In some embodiments of the invention, the second photobioreactor is fixed to the second support stage by a third adjustable clamp.
The device for treating the heavy metal polluted wastewater further comprises an electrophoresis chamber 23. And the wastewater discharged from the water outlet of the second photobioreactor enters the electrophoresis chamber, and metal particles in the wastewater are attached to the surface of the electrode under the action of electrophoresis and finally settle at the bottom of the electrophoresis chamber.
An anode 24 and a cathode 25 are disposed in the electrophoresis chamber. The anode and cathode in the electrophoresis chamber are connected to the voltage controller 8, and the electrophoresis chamber receives the required electric energy from the solar cell panel through the voltage controller. In some embodiments of the invention, the anode and cathode are connected to the voltage controller 8 by a fourth wire 26. In some embodiments of the present invention, the anode material includes, but is not limited to, ruthenium iridium titanium alloy. In some embodiments of the present invention, the cathode material includes, but is not limited to, ruthenium iridium titanium alloy.
The electrophoresis chamber is provided with a water inlet and a water outlet; and the water inlet of the electrophoresis chamber is connected with the water outlet of the plant growth chamber. In some embodiments of the present invention, a fifth valve 22 is disposed at the water inlet of the electrophoresis chamber, and is used for controlling the water outlet of the second photobioreactor to enter the electrophoresis chamber. In some embodiments of the present invention, a sixth valve 30 is disposed at the water outlet of the electrophoresis chamber.
And a precipitation outlet is arranged at the bottom of the electrophoresis chamber. In some embodiments of the invention, the bottom of the electrophoresis chamber is a tapered bottom 27. The conical bottom of the electrophoresis chamber greatly facilitates the recovery of the reduced and precipitated metals. In some embodiments of the invention, the precipitation outlet of the electrophoresis chamber is provided with a fourth valve 21.
In some embodiments of the present invention, the electrophoresis chamber is obtained by welding a rectangular frame and a conical base, and the conical base is a groove body of the electrophoresis chamber. In certain embodiments, the rectangular parallelepiped frame has a length of 9.5cm, a width of 6.0cm, and a height of 6 cm. In some embodiments of the present invention, the rectangular parallelepiped frame is made of acrylic, and the conical base is made of organic glass.
The installation of multiple pairs of electrodes in the electrophoresis chamber may reduce the time to electrophoretically recover reduced metal, possibly because more electrodes provide more surface area to interact with the reduced metal.
In some embodiments of the present invention, a single pair of electrodes is used in the electrophoresis chamber, which can reduce the installation cost of the system. In some embodiments, the voltage applied between the anode and the cathode in the single pair of electrodes is 12V for 24 h.
The treatment device for the heavy metal polluted wastewater further comprises a collecting tank 29. The collection tank is provided with a first sediment inlet. And the first precipitation inlet of the collection tank is connected with the precipitation outlet of the electrophoresis chamber.
In some embodiments of the invention, the first sedimentation inlet of the collection tank is connected to the sedimentation outlet of the electrophoresis chamber by a second conduit 28. The sediment deposited at the bottom of the electrophoresis chamber may enter the collection tank through the second pipe. In some embodiments of the invention, the second tubing is silicone tubing.
In some embodiments of the invention, the collection tank is further provided with a second sedimentation inlet, and the second sedimentation inlet of the collection tank is connected with the sedimentation outlet of the first sedimentation tank.
In some embodiments of the invention, the collection tank is a cuboid-shaped box with a cover, the box is 12cm long, 6cm wide and 6cm high, and the cover of the box with the cover can be detached. In some embodiments of the present invention, the material of the collecting tank is polyvinyl chloride (PVC).
The device for treating the heavy metal polluted wastewater further comprises a first sedimentation tank 31. And the water discharged from the electrophoresis chamber enters a first sedimentation tank, and sedimentation is carried out in the first sedimentation tank.
The first sedimentation tank is provided with a water inlet and a water outlet. And the water inlet of the first sedimentation tank is connected with the water outlet of the electrophoresis chamber.
In some embodiments of the invention, the first settling tank is further provided with a settling outlet. And the sedimentation outlet of the first sedimentation tank is connected with the second sedimentation inlet of the collection tank.
In some embodiments of the invention, the number of the water outlets of the first sedimentation tank is 3. The method specifically comprises the following steps: a first water outlet, a second water outlet and a third water outlet. In some embodiments, a seventh valve 32 is disposed at the first water outlet of the first sedimentation tank, an eighth valve 33 is disposed at the second water outlet of the first sedimentation tank, and a ninth valve 34 is disposed at the third water outlet of the first sedimentation tank. The function of setting up 3 delivery ports is: 1) draining clean water (if any) without disturbing the precipitated metals;
2) depending on the water level and the level of the precipitate, using the most suitable outlet will help to recover the heavy metals in the precipitate more efficiently.
In certain embodiments of the invention, the bottom of the first settling tank is a conical bottom.
The structure and source of the first sedimentation tank are not particularly limited, and the first sedimentation tank can be a commonly-sold sedimentation tank.
In some embodiments of the present invention, the apparatus for treating heavy metal contaminated wastewater further comprises a second sedimentation tank 36. And the water inlet of the second sedimentation tank is connected with the water outlet of the first sedimentation tank.
In some embodiments of the present invention, the second sedimentation tank is provided with 3 water inlets, specifically including: first water inlet, second water inlet and third water inlet. The first water inlet of the second sedimentation tank is connected with the first water outlet of the first sedimentation tank, the second water inlet of the second sedimentation tank is connected with the second water outlet of the first sedimentation tank, and the third water inlet of the second sedimentation tank is connected with the third water outlet of the first sedimentation tank.
In some embodiments of the present invention, an eleventh valve 37 is disposed at the water outlet of the second sedimentation tank.
In some embodiments of the invention, the water discharged from the water outlet of the second sedimentation tank is treated water.
The structure and source of the second sedimentation tank are not particularly limited, and the second sedimentation tank can be a commonly-sold sedimentation tank.
The present invention is not limited to the kind and source of all the valves, and may be any valve that is generally commercially available.
The present invention is not particularly limited to the kind and source of all the above-mentioned electric wires, and the electric wires may be generally commercially available electric wires.
The invention provides a novel treatment device for purifying a heavy metal polluted water body and enriching and recovering heavy metals. The device has the characteristics of simple operation and low maintenance cost.
The invention also provides a method for treating heavy metal polluted wastewater by adopting the treatment device, which comprises the following steps:
A) mixing the heavy metal polluted wastewater with a green algae culture solution, and culturing under the irradiation of a light source to obtain a treatment solution; the luminous intensity of the light source is 95-105 mu mol m-2s-1；
B) Transferring the treatment fluid to an electrophoresis chamber; applying a voltage of 4-20V between the anode and the cathode, and treating for 18-48 h to obtain a first precipitate and a first supernatant;
C) and transferring the first precipitate to a collection tank, transferring the first supernatant to a first sedimentation tank, and standing for 46-50 h to obtain a second supernatant, namely the treated water body.
The method comprises the steps of mixing heavy metal polluted wastewater with a green algae culture solution, and culturing under the irradiation of a light source to obtain a treatment solution; the luminous intensity of the light source is 95-105 mu mol m-2s-1。
In some embodiments of the invention, the concentration of lead ions in the heavy metal contaminated wastewater is 0.01-200 ppm, and the concentration of copper ions is 0.01-120 ppm. In certain embodiments, the heavy metal contaminated wastewater has a lead ion concentration of 150ppm and a copper ion concentration of 150 ppm. In some embodiments of the invention, the pH value of the heavy metal polluted wastewater is 5-10. In some embodiments, the pH value of the heavy metal polluted wastewater is 7-8 or 8.
In some embodiments of the present invention, the green algae in the green algae culture solution is a green algae culture solution with a preservation number of CCTCC No: m20211083 green algae and/or green algae with preservation number of CCTCC No: m20211084 green algae.
In certain embodiments of the invention, the green algae culture is prepared according to the following method:
under the illumination, culturing the green algae in a sterilized liquid culture medium at 25-40 ℃ until the logarithmic phase of the growth of the green algae to obtain a green algae culture solution; the luminous intensity of the illumination is 95-105 mu mol m-2s-1。
In certain embodiments of the invention, the incubation time is 8-12 days. In certain embodiments, the temperature of the incubation is 25 ℃ for 10 days. In certain embodiments of the present invention, the illumination has a luminous intensity of 100 μmol m- 2s-1。
In some embodiments of the invention, the green algae culture solution has an Optical Density (OD) of 0.3-0.5.
In certain embodiments of the invention, the liquid medium is prepared according to the following method:
a1) mixing a sea salt solution with tris (hydroxymethyl) aminomethane to obtain a first mixed solution; in the first mixed solution, the concentration of sea salt is 35g/L, and the concentration of tris (hydroxymethyl) aminomethane is 1.21 g/L;
a2) adjusting the pH value of the first mixed solution to 7.5-8, and sterilizing at 120-122 ℃ for 18-22 min to obtain a second mixed solution;
a3) mixing sodium nitrate, sodium dihydrogen phosphate monohydrate and a trace element solution, sterilizing at 120-122 ℃ for 13-17 min, and adding the mixture into the second mixed solution to obtain a third mixed solution; in the second mixed solution, the addition amount of sodium nitrate is 5g/L, the addition amount of sodium dihydrogen phosphate monohydrate is 5g/L, and the addition amount of a trace element solution is 1 g/L;
the trace element solution is prepared by mixing raw materials including copper sulfate pentahydrate, sodium molybdate dihydrate, zinc sulfate heptahydrate, cobalt chloride hexahydrate and manganese chloride tetrahydrate, and sterilizing at 120-122 ℃ for 18-22 min;
in the trace element solution, the concentration of copper sulfate pentahydrate is 19.6g/L, the concentration of sodium molybdate dihydrate is 12.6g/L, the concentration of zinc sulfate heptahydrate is 44.0g/L, the concentration of cobalt chloride hexahydrate is 10.92g/L, and the concentration of manganese chloride tetrahydrate is 360 g/L.
Step a 1):
in certain embodiments of the invention, the sea salt solution is prepared according to the following method:
sea salt was dissolved in distilled water and vacuum filtered through 0.45 μm pore size filter paper to obtain a sea salt solution.
In some embodiments of the invention, the ratio of the sea salt to the distilled water is 30-40 g: 900-1100 mL. In certain embodiments, the amount ratio of sea salt to distilled water is 35 g: 1000 mL.
Step a 2):
in some embodiments of the present invention, the reagent for adjusting the pH of the first mixed solution is hydrochloric acid.
In some embodiments of the invention, the sterilization pressure is 0.05-0.15 MPa.
In certain embodiments of the invention, the temperature of sterilization is 121 ℃, the pressure is 0.1MPa, and the time is 20 min.
Step a 3):
in some embodiments of the invention, the sodium nitrate, the sodium dihydrogen phosphate monohydrate and the trace element solution are mixed, and the sterilization pressure is 0.05-0.15 MPa.
In certain embodiments of the invention, sodium nitrate, sodium dihydrogen phosphate monohydrate, and the trace element solution are mixed and sterilized at 121 ℃ for 15min under a pressure of 0.1 MPa.
In some embodiments of the invention, the pressure for sterilization is 0.05-0.15 MPa during the preparation of the trace element solution.
In some embodiments of the invention, the temperature of sterilization is 121 ℃ and the time is 20min, and the pressure of sterilization is 0.1MPa during the preparation of the trace element solution.
After the green algae culture solution is obtained, mixing the heavy metal polluted wastewater with the green algae culture solution, and culturing under the irradiation of a light source to obtain a treatment solution; the lightThe source has a luminous intensity of 95 to 105 [ mu ] mol m-2s-1。
In some embodiments of the invention, the volume ratio of the heavy metal contaminated wastewater to the green algae culture solution is 750-850: 80-120 parts. In some embodiments, the volume ratio of the heavy metal contaminated wastewater to the green algae culture solution is 800: 100.
in some embodiments of the present invention, the OD of the mixed solution after the heavy metal contaminated wastewater is mixed with the green algae culture solution7500.3 to 0.5. In some embodiments, the OD of the mixed solution after the heavy metal contaminated wastewater is mixed with the green algae culture solution750Is 0.4.
In some embodiments of the invention, the culturing is performed under stirring at a rotation speed of 18-22 rpm. In certain embodiments, the rotational speed of the agitation is 20 rpm.
In some embodiments of the invention, the temperature of the culture is 24-35 ℃ and the time is 168-192 h. In certain embodiments, the temperature of the incubation is 25 ℃ for 168 hours.
In some embodiments of the invention, the light source has a luminous intensity of 100 μmol m-2s-1。
After the treatment liquid is obtained, transferring the treatment liquid to an electrophoresis chamber; and applying a voltage of 4-20V between the anode and the cathode, and treating for 18-48 h to obtain a first precipitate and a first supernatant.
In some embodiments of the invention, the voltage is 12V, and the processing time is 18-24 h or 24 h.
And after obtaining a first precipitate and a first supernatant, transferring the first precipitate to a collection tank, transferring the first supernatant to a first sedimentation tank, and standing for 46-50 h to obtain a second supernatant, namely the treated water body.
In certain embodiments of the invention, the time of standing is 48 hours.
In some embodiments of the present invention, the second precipitate obtained by standing is transferred to a collection tank, the second supernatant is transferred to a second sedimentation tank, and after standing, a third supernatant is obtained, which is the treated water body; in some embodiments, the standing time is 24-48 hours or 24 hours.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
In order to further illustrate the present invention, the following will describe the apparatus and method for treating heavy metal contaminated wastewater in detail with reference to the examples, but should not be construed as limiting the scope of the present invention.
The raw material sources used in the examples are generally commercially available.
The green algae in the embodiment comprises a green algae with a preservation number of CCTCC No: m20211083 green algae and the preservation number is CCTCC No: m20211084 green algae.
Example 1
The treatment device for the heavy metal polluted wastewater shown in FIG. 1 is adopted to treat the heavy metal polluted wastewater, and comprises the following steps:
1. the liquid medium was prepared as follows:
a1) dissolving 35g of sea salt in 1000mL of distilled water, and performing vacuum filtration by using filter paper with the aperture of 0.45 mu m to obtain a sea salt solution; mixing a sea salt solution with tris (hydroxymethyl) aminomethane to obtain a first mixed solution; in the first mixed solution, the concentration of sea salt is 35g/L, and the concentration of tris (hydroxymethyl) aminomethane is 1.21 g/L;
a2) adjusting the pH value of the first mixed solution to 8 by using hydrochloric acid, and sterilizing at 121 ℃ and under high pressure of 0.1MPa for 20min to obtain a second mixed solution;
a3) mixing sodium nitrate, sodium dihydrogen phosphate monohydrate and the trace element solution, sterilizing at 121 ℃ under high pressure of 0.1MPa for 15min, and adding into the second mixed solution to obtain a third mixed solution; in the second mixed solution, the addition amount of sodium nitrate is 5g/L, the addition amount of sodium dihydrogen phosphate monohydrate is 5g/L, and the addition amount of a trace element solution is 1 g/L;
the microelement solution is prepared by mixing raw materials including copper sulfate pentahydrate, sodium molybdate dihydrate, zinc sulfate heptahydrate, cobalt chloride hexahydrate and manganese chloride tetrahydrate, and sterilizing at 121 deg.C under high pressure of 0.1MPa for 20 min;
in the trace element solution, the concentration of copper sulfate pentahydrate is 19.6g/L, the concentration of sodium molybdate dihydrate is 12.6g/L, the concentration of zinc sulfate heptahydrate is 44.0g/L, the concentration of cobalt chloride hexahydrate is 10.92g/L, and the concentration of manganese chloride tetrahydrate is 360 g/L.
2. The green algae culture solution is prepared according to the following method:
under the illumination, culturing green algae in the sterilized liquid culture medium at 25 ℃ for 10d to obtain a green algae culture solution; the luminous intensity of the illumination is 100 mu mol m-2s-1。
3. The treatment method of the heavy metal polluted wastewater comprises the following steps:
in the heavy metal polluted wastewater, the concentration of lead ions is 150ppm, and the concentration of copper ions is 150 ppm; the pH value of the heavy metal polluted wastewater is 8;
3-1) mixing 800mL of heavy metal polluted wastewater with 100mL of green algae culture solution, and then obtaining the OD of the mixed solution750Culturing for 7d at 25 ℃ under the irradiation of a light source, wherein the stirring speed is 20rpm in the culturing process to obtain a treatment solution, wherein the temperature is 0.4 ℃; the luminous intensity of the light source is 100 mu mol m-2s-1；
3-2) transferring the treatment liquid to an electrophoresis chamber after obtaining the treatment liquid; applying a voltage of 12V between the anode and the cathode, and treating for 24h to obtain a first precipitate and a first supernatant;
3-3) transferring the first precipitate to a collection tank, transferring the first supernatant to a first sedimentation tank, and standing for 48 hours to obtain a second supernatant and a second precipitate;
and 3-4) transferring the second precipitate to a collection tank, transferring the second supernatant to a second sedimentation tank, and standing for 24 hours to obtain a third supernatant which is the treated water body.
And (3) detecting the treated water body by using a plasma mass spectrometry (ICP-MS), wherein an experimental result shows that the removal efficiency of lead ions and copper ions in the treated water body is 99.2% and 98.2%, respectively.
Experimental results show that when the treatment device and the treatment method are used for treating the heavy metal polluted wastewater, the removal rate of heavy metal ions in the treated water body is high.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A treatment device for heavy metal contaminated wastewater, comprising:
a reservoir;
a first photobioreactor; a glass tube is arranged in the first photobioreactor; one end of the glass tube is connected with an air pump and is used for providing air for the green algae culture solution in the first photobioreactor;
heavy metal polluted wastewater discharged from a water outlet of the reservoir is mixed with green algae culture solution discharged from a green algae culture solution outlet of the first photobioreactor and then enters a second photobioreactor;
an electrophoresis chamber; an anode and a cathode are arranged in the electrophoresis chamber; the electrophoresis chamber is provided with a water inlet and a water outlet; a sediment outlet is arranged at the bottom of the electrophoresis chamber; the water inlet of the electrophoresis chamber is connected with the water outlet of the second photobioreactor;
the first sedimentation tank is connected with a water outlet of the electrophoresis chamber; the first sedimentation tank is provided with a water outlet; the treated water body is discharged from a water outlet of the first sedimentation tank;
a collection tank provided with a first precipitation inlet; and the first precipitation inlet of the collection tank is connected with the precipitation outlet of the electrophoresis chamber.
2. The processing device of claim 1, further comprising a solar panel and a voltage controller;
the air pump receives required electric energy from the solar panel through the voltage controller;
and the anode and the cathode in the electrophoresis chamber are connected with the voltage controller, and the electrophoresis chamber receives required electric energy from the solar panel through the voltage controller.
3. The processing apparatus according to claim 1, wherein an agitator is provided in the second photobioreactor;
the stirrer is connected with an electric motor; the electric motor receives the required electric power from the solar panel through the voltage controller.
4. The processing device according to claim 1, wherein the bottom of the electrophoresis chamber is a tapered bottom.
5. The treatment apparatus according to claim 1, wherein the bottom of the first settling tank is a tapered bottom.
6. A method for treating heavy metal contaminated wastewater using the treatment apparatus of claim 1, comprising the steps of:
A) mixing the heavy metal polluted wastewater with a green algae culture solution, and culturing under the irradiation of a light source to obtain a treatment solution; the luminous intensity of the light source is 95-105 mu mol m-2s-1；
B) Transferring the treatment fluid to an electrophoresis chamber; applying a voltage of 4-20V between the anode and the cathode, and treating for 18-48 h to obtain a first precipitate and a first supernatant;
C) and transferring the first precipitate to a collection tank, transferring the first supernatant to a first sedimentation tank, and standing for 46-50 h to obtain a second supernatant, namely the treated water body.
7. The method according to claim 6, wherein the concentration of lead ions in the heavy metal polluted wastewater is 0.01-200 ppm, and the concentration of copper ions is 0.01-120 ppm;
the pH value of the heavy metal polluted wastewater is 5-10.
8. The method of claim 6, wherein the green algae culture is prepared by the following method:
under the illumination, culturing the green algae in a sterilized liquid culture medium at 25-40 ℃ until the logarithmic phase of the growth of the green algae to obtain a green algae culture solution; the luminous intensity of the illumination is 95-105 mu mol m-2s-1；
The green algae in the green algae culture solution is the green algae with the preservation number of CCTCC No: m20211083 green algae and/or green algae with preservation number of CCTCC No: m20211084 green algae.
9. The method according to claim 8, wherein the liquid medium is prepared by the following method:
a1) mixing a sea salt solution with tris (hydroxymethyl) aminomethane to obtain a first mixed solution; in the first mixed solution, the concentration of sea salt is 35g/L, and the concentration of tris (hydroxymethyl) aminomethane is 1.21 g/L;
a2) adjusting the pH value of the first mixed solution to 7.5-8, and sterilizing at 120-122 ℃ for 18-22 min to obtain a second mixed solution;
a3) mixing sodium nitrate, sodium dihydrogen phosphate monohydrate and a trace element solution, sterilizing at 120-122 ℃ for 13-17 min, and adding the mixture into the second mixed solution to obtain a third mixed solution; in the second mixed solution, the addition amount of sodium nitrate is 5g/L, the addition amount of sodium dihydrogen phosphate monohydrate is 5g/L, and the addition amount of a trace element solution is 1 g/L;
the trace element solution is prepared by mixing raw materials including copper sulfate pentahydrate, sodium molybdate dihydrate, zinc sulfate heptahydrate, cobalt chloride hexahydrate and manganese chloride tetrahydrate, and sterilizing at 120-122 ℃ for 18-22 min;
in the trace element solution, the concentration of copper sulfate pentahydrate is 19.6g/L, the concentration of sodium molybdate dihydrate is 12.6g/L, the concentration of zinc sulfate heptahydrate is 44.0g/L, the concentration of cobalt chloride hexahydrate is 10.92g/L, and the concentration of manganese chloride tetrahydrate is 360 g/L.
10. The method as claimed in claim 6, wherein the OD of the mixed solution of the heavy metal contaminated wastewater and the green algae culture solution in the step A)7500.3 to 0.5;
the culture is carried out under the condition of stirring, and the rotating speed of the stirring is 18-22 rpm;
the culture temperature is 24-35 ℃, and the culture time is 168-192 hours.
CN202111574776.0A 2021-12-21 2021-12-21 Treatment device and method for heavy metal polluted wastewater Active CN114163086B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202111574776.0A CN114163086B (en) 2021-12-21 2021-12-21 Treatment device and method for heavy metal polluted wastewater
PCT/CN2021/141907 WO2023115607A1 (en) 2021-12-21 2021-12-28 Treatment apparatus and method for heavy metal-polluted wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111574776.0A CN114163086B (en) 2021-12-21 2021-12-21 Treatment device and method for heavy metal polluted wastewater

Publications (2)

Publication Number Publication Date
CN114163086A true CN114163086A (en) 2022-03-11
CN114163086B CN114163086B (en) 2023-04-07

Family

ID=80487715

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111574776.0A Active CN114163086B (en) 2021-12-21 2021-12-21 Treatment device and method for heavy metal polluted wastewater

Country Status (2)

Country Link
CN (1) CN114163086B (en)
WO (1) WO2023115607A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1930820A1 (en) * 1968-06-17 1970-02-12 M & T Chemicals Inc Process for making a metal plating
CN103833144A (en) * 2014-01-06 2014-06-04 东北大学 Method for removing heavy metal ions in water by using fermentation broth of bacterium producing flocculant
CN109576160A (en) * 2017-09-29 2019-04-05 武汉藻优生物科技有限公司 A kind of energy removes chlorella W3 and its application of the heavy metal in high content of beary metal water body
CN113264617A (en) * 2021-05-28 2021-08-17 大连海事大学 Dielectrophoresis-assisted radioactive marine sewage microalgae cleaning device and method

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100267085A1 (en) * 2007-06-29 2010-10-21 The Arizona Board Of Regents, A Body Corporate Acting On Behalf Of Arizona State University Novel pseudochlorococcum species and uses therefor
CN101130134B (en) * 2007-07-17 2011-08-31 四川大学 Technique for processing plants in high rich of heavy metal by using mushroom fungus
US9315403B1 (en) * 2012-12-04 2016-04-19 Eldorado Biofuels, LLC System for algae-based treatment of water
CN106892529A (en) * 2015-12-18 2017-06-27 王冰 A kind of many technology coupling purification high salt water systems based on microalgae
CN110699252A (en) * 2019-11-08 2020-01-17 安徽德宝生物科技有限公司 Algae continuous culture reaction system
CN112707509B (en) * 2020-11-10 2022-06-21 烟台大学 Method for removing heavy metals in water body by using marine microalgae

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1930820A1 (en) * 1968-06-17 1970-02-12 M & T Chemicals Inc Process for making a metal plating
CN103833144A (en) * 2014-01-06 2014-06-04 东北大学 Method for removing heavy metal ions in water by using fermentation broth of bacterium producing flocculant
CN109576160A (en) * 2017-09-29 2019-04-05 武汉藻优生物科技有限公司 A kind of energy removes chlorella W3 and its application of the heavy metal in high content of beary metal water body
CN113264617A (en) * 2021-05-28 2021-08-17 大连海事大学 Dielectrophoresis-assisted radioactive marine sewage microalgae cleaning device and method

Also Published As

Publication number Publication date
WO2023115607A1 (en) 2023-06-29
CN114163086B (en) 2023-04-07

Similar Documents

Publication Publication Date Title
CN104496094B (en) A kind of high-risk wastewater treatment instrument in laboratory and treatment process
CN103508637B (en) Traditional Chinese medicine wastewater treatment system and method for treating traditional Chinese medicine wastewater
CN101781001A (en) Method for processing effluent by two-stage electrolysis and device thereof
CN105152422A (en) System for treating heavy metal wastewater by electrochemical-microflocculation-floatation process
CN106430746A (en) Process for pretreating natural gas produced water with electric flocculation
CN110040884A (en) A kind of sewage reclaiming method for electroplating industry
CN102642955A (en) Electrochemical removal method for heavy metals in breeding circulating seawater
CN107285435A (en) Double electrolysis remove the method and apparatus of the phosphorus in organophosphorus pesticide production waste water
CN113651470A (en) Novel biomass waste disposal and resource utilization system and method
CN105585224A (en) Treatment system for removing heavy metals in industrial wastewater
CN114163086B (en) Treatment device and method for heavy metal polluted wastewater
CN102887606A (en) Garbage leachate treatment method using direct current flocculation-MBR (membrane bioreactor)
CN104310667B (en) A kind of device of repairing heavy metal cadmium in underground water
CN107176729A (en) A kind of AEC electric flocculations waste water treatment process
CN202449955U (en) Integrated treatment device for landfill leachate
CN105776684B (en) A kind of method that urban wastewater treatment and resource recycling utilize
KR101778259B1 (en) Effluent Treatment Apparatus Comprising Nanocatalytic Anode Plate and Cathode Plate for Phosphorus Removal by Electrolysis Floating and Flocculation Process and Treatment Method Using the Same
CN106430870B (en) A kind of system and method for strengthening excess sludge recycling
CN201240894Y (en) Electrochemical waste water treatment device
CN103787467A (en) Equipment and process for treating nickel-cobalt wastewater in hydrometallurgy industry through electrolytic method
CN1629079A (en) Electrochemical method and apparatus for removing organic substances from water
KR102015446B1 (en) An Wastewater Disposal Method Capable of Removing Microalgae, Extracellular Polymer Materials, and Cyanide Compounds
CN204325051U (en) The high-risk wastewater treatment instrument in a kind of laboratory
CN208649050U (en) A kind of electroplating waste-water reutilizing treatment combined device
CN112062281A (en) Method for repairing arsenic pollution of saline-alkali water body by using blue algae-biomembrane complex

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant