CN110976505A - Method and device for rapidly electrically repairing heavy metal contaminated soil by using magnetic biochar - Google Patents

Method and device for rapidly electrically repairing heavy metal contaminated soil by using magnetic biochar Download PDF

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Publication number
CN110976505A
CN110976505A CN201911305193.0A CN201911305193A CN110976505A CN 110976505 A CN110976505 A CN 110976505A CN 201911305193 A CN201911305193 A CN 201911305193A CN 110976505 A CN110976505 A CN 110976505A
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China
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soil
adsorption
groove
magnetic biochar
heavy metal
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CN201911305193.0A
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Chinese (zh)
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张棋
叶雪珠
陈德
肖文丹
赵首萍
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Zhejiang Academy of Agricultural Sciences
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Zhejiang Academy of Agricultural Sciences
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • B09C1/085Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/02Extraction using liquids, e.g. washing, leaching, flotation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00In situ

Abstract

The invention discloses a method and a device for quickly electrically repairing polluted soil by using magnetic biochar, and belongs to the technical field of quick soil repair. The method comprises the steps of preparing magnetic biochar with sludge, then digging an adsorption groove in the soil polluted by heavy metal to be repaired, paving the magnetic biochar in the adsorption groove, then burying a positive electrode and a negative electrode in the soil on two sides of the adsorption groove, electrifying, constructing a repairing electric field, and finally watering the soil to start rapid repairing. The invention can solve the problems that the prior heavy metal non-point source pollution is easy to bring in new pollution medium or pollution source, has high repair difficulty and high cost, and lacks of application methods and equipment.

Description

Method and device for rapidly electrically repairing heavy metal contaminated soil by using magnetic biochar
Technical Field
The invention belongs to the technical field of soil rapid remediation, and particularly relates to a method and a device for rapidly electrically remediating polluted soil by using magnetic biochar.
Background
The heavy metal contaminated soil in the prior art has great difficulty in remediation, the main difficulty is that the heavy metal contamination of farmlands mostly belongs to non-point source contamination, the contamination exists in hundreds of thousands of acres of land in the first occurrence, the prior art lacks of a method and a device capable of low-cost and rapid treatment, the common technology is shown in the following patents, the application No. CN201510971681.0 is named as an electric remediation strengthening device and a method for removing heavy metal in sludge by using the device, the application No. 201811446910.7 is named as a method for strengthening electric-chemical oxidation remediation of organic contaminated soil by using magnetic sludge carbon, the remediation methods and the devices in the two patents have great problems, one is that the two patents can only be applied in a laboratory, the difficulty is great if the heavy metal contaminated soil is applied to non-point source contamination, the cost is very high, the other is that the remediation process needs to be carried out operations such as acid pickling or directly mixing a treatment medium with the soil, and the, essentially carries another contaminated medium in; finally, the whole biomass charcoal is complex in preparation, use method, repairing operation and operation, and cannot be applied to the heavy metal non-point source pollution in practical application.
Disclosure of Invention
Aiming at the problems that the prior heavy metal non-point source pollution is easy to bring in a new pollution medium or a new pollution source, has high repairing difficulty and high cost and lacks an application method and equipment, the invention aims to provide a method and a device for quickly electrically repairing polluted soil by using magnetic biochar.
The invention provides a method for quickly electrically repairing polluted soil by using magnetic biochar, which comprises the steps of preparing magnetic biochar containing magnetism by using sludge, then digging an adsorption groove in the heavy metal polluted soil to be repaired, paving the magnetic biochar in the adsorption groove, then embedding a positive electrode and a negative electrode in the soil on two sides of the adsorption groove, electrifying, constructing a repairing electric field, and finally watering the soil to start quick repairing.
The method for rapidly electrically repairing the heavy metal contaminated soil by using the magnetic biochar is preferably set as follows:
and (2) coating the dried sludge in a boron nitride crucible to prepare an MBCA (moving bed biofilm carrier) film, then putting the crucible in a muffle furnace for pyrolysis at the pyrolysis temperature of 400-700 ℃, keeping for 1h, then transferring the crucible to a vacuum dryer for cooling, collecting solids, and uniformly mixing the obtained solids for later use before storing in the dryer.
The method for rapidly electrically repairing the heavy metal contaminated soil by using the magnetic biochar is further preferably set to be that the pyrolysis temperature in the muffle furnace is 400 ℃ or 500 ℃ or 600 ℃ or 700 ℃, and the pyrolysis reaction rate is 3 ℃ min-1.
The method for rapidly electrically restoring the heavy metal contaminated soil by using the magnetic biochar is further preferably set to be that dry sludge is put into a quartz boat, the quartz boat is pyrolyzed in a quartz tube resistance furnace and is in an N2 atmosphere, the pyrolysis temperature ranges from 400 ℃ to 700 ℃, the quartz boat is kept for 1h, after cooling, the quartz boat is taken out from the furnace, solids are collected, and the obtained solids are uniformly mixed for later use before being stored in a dryer.
The method for rapidly electrically repairing the heavy metal contaminated soil by using the magnetic biochar is preferably set to be that the gas quantity of the N2 is 200 Ml/min.
The method for rapidly electrically restoring the heavy metal contaminated soil by using the magnetic biochar is preferably set to be that the pyrolysis temperature in the resistance furnace is 400 ℃ or 500 ℃ or 600 ℃ or 700 ℃.
The method for rapidly electrically repairing the heavy metal contaminated soil by using the magnetic biochar is further preferably set as follows:
s1, preparing magnetic biochar;
s2, preparing an adsorption component, wherein the adsorption component contains the magnetic biochar and a filter screen wrapping the magnetic biochar;
s3, excavating adsorption grooves, excavating at least one adsorption groove in the heavy metal polluted soil to be repaired, and paving the adsorption component in the groove;
s4, constructing a repairing electric field which consists of a positive electrode and a negative electrode buried in soil on two sides of the adsorption groove;
s5, hanging a spraying component, wherein the spraying component is hung above the soil on one side of the adsorption groove and comprises spray heads uniformly distributed for spraying water;
s6, spraying water, starting a spraying assembly, and gradually dissolving metal ions in the soil in water;
s7, passing the metal ions through the adsorption component arranged in the groove under the action of the electric field, and adsorbing and purifying the metal ions by the magnetic biochar;
s7, switching off the power supply, taking out the adsorption component and the positive and negative electrodes, taking out the magnetic biochar in the adsorption component, and performing centralized treatment;
s8, repeating the steps 1-7 for at least 1 time, and then detecting the heavy metal residual quantity in the soil until the heavy metal residual quantity reaches the standard.
The method for rapidly electrically repairing the heavy metal contaminated soil by using the magnetic biochar is further preferably set as follows:
s21, preparing magnetic biochar;
s22, preparing an adsorption component, wherein the adsorption component contains the magnetic biochar and a filter screen wrapping the magnetic biochar;
s31, excavating the soil to be repaired, constructing an inclined bottom groove, paving a bottom plate at the bottom of the inclined bottom groove, and then backfilling the soil to be repaired;
s32, digging at least one adsorption groove in the backfilled soil polluted by the heavy metal to be repaired, and paving the adsorption component in the groove;
s24, constructing a repairing electric field which consists of a positive electrode and a negative electrode buried in soil on two sides of the adsorption groove;
s25, hanging a spraying component, wherein the spraying component is hung above the soil on one side of the adsorption groove and comprises spray heads uniformly distributed for spraying water;
s26, spraying water, starting a spraying assembly, and gradually dissolving metal ions in the soil in water;
s27, passing the metal ions through the adsorption component arranged in the groove under the action of the electric field, and adsorbing and purifying the metal ions by the magnetic biochar;
s28, switching off the power supply, taking out the adsorption component and the positive and negative electrodes, taking out the magnetic biochar in the adsorption component, and performing centralized treatment;
s29, repeating the steps 1-7 for at least 1 time, and then detecting the heavy metal residual quantity in the soil until the heavy metal residual quantity reaches the standard.
Another object of the present invention is to provide a device for rapidly electrically repairing contaminated soil by magnetic biochar, which is applied to the above repairing method, and comprises a first positive electrode, a first negative electrode, a first adsorption component, an adsorption groove, and a spraying component; the adsorption assembly comprises a filter frame, an adsorption bag capable of being taken out quickly is arranged in the filter frame, and the adsorption bag is wrapped with the magnetic biochar.
The device for rapidly electrically repairing heavy metal contaminated soil by using the magnetic biochar is further preferably arranged in a way that a bottom plate obliquely inserted into the soil is further arranged at the bottom of the adsorption component, one end of the bottom plate is provided with a hanging ring, the other end of the bottom plate is provided with a backflow tank, a backflow pipe is arranged on the backflow tank, penetrates through the bottom plate and is connected with external water pumping equipment, a water level meter is arranged on the backflow tank, the water level meter is communicated with a controller through a circuit arranged in the bottom plate, the controller is connected with and controls the water pumping equipment through the circuit, an outlet of the water pumping equipment is connected with a three-way valve, and the three-way valve is communicated with the spraying component through.
Advantageous effects
The method and the device for rapidly electrically repairing the heavy metal contaminated soil by using the magnetic biochar have the following advantages:
1. according to the invention, the recyclable magnetic biochar is used, strong acid is not needed to be used for cleaning the soil, and new pollution media or pollution source heavy metal non-point source pollution can be prevented from being brought into the soil, so that the remediation is finished.
2. The invention does not need to take out the soil and transport the soil back to be treated, and directly repairs the soil in situ, and has small difficulty and low cost in the whole repair.
3. The invention can greatly reduce the processing steps and realize high efficiency by in-situ field repair and a convenient device.
4. The invention has high removal efficiency of the whole heavy metal by using a mode of combining the magnetic biochar with electric repair.
5. The magnetic biochar uses the coagulation dephosphorization sludge in the sedimentation tank, the sludge is the coagulation sludge containing iron and CPAM, the raw material source is sufficient, the problem of the existing sludge treatment can be solved, and meanwhile, the cost is low.
6. The magnetic biochar disclosed by the invention is simple in whole preparation process, and the whole repair cost can be effectively reduced.
7. The magnetic biochar disclosed by the invention is a crystal containing α iron and a crystal containing β iron, both of the crystals have the advantages of strong adsorption effect, rapidness in repair and low manufacturing cost, and can be used independently or in combination.
Drawings
Fig. 1 is a schematic diagram of a first embodiment.
Fig. 2 is a schematic view of a second embodiment.
Fig. 3 is a schematic view of the bottom plate of fig. 2.
Fig. 4 is a comparison of two magnetic biomass charcoals.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and with reference to the attached drawings.
Example 1
The preparation method comprises the following steps of taking sludge as a raw material, carrying out two different pyrolysis processes on the magnetic biochar, putting the dried sludge into a boron nitride crucible and coating by about 50g to prepare an MBCA (moving bed biofilm reactor) membrane, then putting the crucible into a muffle furnace, carrying out pyrolysis at a designed temperature (400, 500, 600 and 700 ℃), keeping the reaction rate at 3 ℃ for min-1, then transferring the crucible into a vacuum dryer to cool for 1h, and finally dividing the sample into MBCA-400, MBCA-500, MBCA-600 and MBCA-700 according to the pyrolysis peak temperature of the sample.
Example 2
The MBCN was prepared by another method, in which about 50g of dry sludge was loaded into a quartz boat, pyrolyzed in a quartz tube resistance furnace under an atmosphere of N2 (200 Ml/min airflow) at four alternating peak temperatures of 400 ℃, 500 ℃, 600 ℃ and 700 ℃ and kept constant for 1h, after cooling, the quartz boat was taken out of the furnace, and solid samples, MBCN-400, MBCN-500, MBCN-600 and MBCN-700, respectively, were collected, followed by three replicates showing pyrolysis peak temperatures, all pyrolysis experiments were repeated, and the resulting samples were uniformly mixed before being stored in a desiccator for further use.
Example 3
Firstly, constructing a device for rapidly electrically repairing polluted soil by magnetic biochar according to a figure 1, wherein the device comprises a first positive electrode 1, a first negative electrode 4, a first adsorption component 3, an adsorption groove and a spraying component 2; the adsorption component comprises a filter frame, an adsorption bag which can be quickly taken out is arranged in the filter frame, and magnetic biochar is wrapped in the adsorption bag. The device is combined with magnetic biochar to form a method for quickly electrically repairing heavy metal contaminated soil, the method comprises the steps of preparing magnetic biochar containing magnetism by using sludge, then digging an adsorption groove in the heavy metal contaminated soil to be repaired, paving the magnetic biochar in the adsorption groove, then embedding a positive electrode and a negative electrode in the soil on the two sides of the adsorption groove, electrifying, constructing a repairing electric field, and finally watering the soil to start quick repairing. Under the action of the electric field, the metal particles or metal ions 5 are combined with water in the soil particles 6 and rapidly move in the direction of the biological activated carbon in the water and are captured by the biological activated carbon.
In this embodiment, as a preferred implementation, the repairing method specifically includes the following steps:
s1, preparing magnetic biochar;
s2, preparing an adsorption component, wherein the adsorption component contains magnetic biochar and a filter screen wrapping the magnetic biochar;
s3, excavating adsorption grooves, excavating at least one adsorption groove in the heavy metal polluted soil to be repaired, and paving an adsorption component in the groove;
s4, constructing a repairing electric field which consists of a positive electrode and a negative electrode buried in soil on two sides of the adsorption groove;
s5, hanging a spray component 2, hanging the spray component 2 above the soil on one side of the adsorption groove, wherein the spray component 2 comprises spray heads uniformly distributed for spraying water;
s6, spraying water, starting the spraying assembly 2, and gradually dissolving metal ions in the soil in the water;
s7, passing the metal ions through the adsorption component arranged in the groove under the action of the electric field, and adsorbing and purifying the metal ions by the magnetic biochar;
s7, switching off the power supply, taking out the adsorption component and the positive and negative electrodes, taking out the magnetic biochar in the adsorption component, and performing centralized treatment; the centralized treatment can be used for centralized landfill in unmanned areas or deep sea or other centralized treatment methods, such as roadbed materials and the like.
S8, repeating the steps 1-7 for at least 1 time, and then detecting the heavy metal residual quantity in the soil until the heavy metal residual quantity reaches the standard.
Example 4
Another magnetic charcoal device for rapidly electrically repairing polluted soil by magnetic charcoal is constructed as shown in fig. 2, and comprises a second positive electrode 11, a second negative electrode 41, a second adsorption component 31, an adsorption groove and a spraying component 2; the adsorption component comprises a filter frame, an adsorption bag which can be quickly taken out is arranged in the filter frame, and magnetic biochar is wrapped in the adsorption bag. The bottom of adsorption component still is equipped with the bottom plate 7 that the slope inserted in soil, 7 one end of bottom plate is provided with rings 9, the other end is equipped with backwash tank 10 and water-collecting cavity 11, be equipped with back flow 8 on the backwash tank, the back flow runs through bottom plate 7 and links to each other with outside pumping equipment, be equipped with fluviograph 12 on the backwash tank, the fluviograph is linked together with the controller through the circuit of locating in bottom plate 7, the controller passes through circuit connection and control pumping equipment, pumping equipment's export links to each other with the three-way valve, the three-way valve is linked together with the spray assembly through.
The difference between the embodiment 4 and the embodiment 3 is that the bottom plate 7 is laid at the bottom of the surface contaminated soil, and the bottom plate 7 can be quickly taken out and recycled after the restoration is completed. Meanwhile, the bottom plate 7 is provided with a return pipe and a monitoring probe, so that whether the polluted water which needs to be gathered is secondarily adsorbed again can be determined according to the specific water content.
The device is combined with magnetic biochar to form a method for quickly electrically repairing heavy metal contaminated soil, and the method comprises the following specific steps:
s21, preparing magnetic biochar;
s22, preparing an adsorption component, wherein the adsorption component contains magnetic biochar and a filter screen wrapping the magnetic biochar;
s31, excavating the soil to be repaired, constructing an inclined bottom groove, paving a bottom plate 7 at the bottom of the inclined bottom groove, and then backfilling the soil to be repaired;
s32, excavating at least one adsorption groove in the backfilled heavy metal contaminated soil to be repaired, and paving an adsorption component in the groove;
s24, constructing a repairing electric field which consists of a positive electrode and a negative electrode buried in soil on two sides of the adsorption groove;
s25, hanging a spray component 2, hanging the spray component 2 above the soil on one side of the adsorption groove, wherein the spray component 2 comprises spray heads uniformly distributed for spraying water;
s26, spraying water, starting the spraying assembly 2, and gradually dissolving metal ions in the soil in the water;
s27, enabling the metal ions to penetrate through the adsorption component arranged in the groove under the action of an electric field, wherein an arrow is a migration direction, and the metal ions are adsorbed and purified by the magnetic biochar;
s28, switching off the power supply, taking out the adsorption component and the positive and negative electrodes, taking out the magnetic biochar in the adsorption component, and performing centralized treatment;
s29, repeating the steps 1-7 for at least 1 time, and then detecting the heavy metal residual quantity in the soil until the heavy metal residual quantity reaches the standard.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the examples, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (10)

1. The method for rapidly electrically repairing the heavy metal contaminated soil by using the magnetic biochar is characterized in that the magnetic biochar containing magnetism is prepared by using sludge, then an adsorption groove is dug in the heavy metal contaminated soil to be repaired, the magnetic biochar is laid in the adsorption groove, then a positive electrode and a negative electrode are buried in the soil on the two sides of the adsorption groove, a repairing electric field is powered on and constructed, and finally, the soil is watered to begin rapid repairing.
2. The method according to claim 1, wherein the magnetic biochar preparation method comprises the following steps:
and (2) coating the dried sludge in a boron nitride crucible to prepare an MBCA (moving bed biofilm carrier) film, then putting the crucible in a muffle furnace for pyrolysis at the pyrolysis temperature of 400-700 ℃, keeping for 1h, then transferring the crucible to a vacuum dryer for cooling, collecting solids, and uniformly mixing the obtained solids for later use before storing in the dryer.
3. Method according to claim 2, characterized in that the method steps are as follows: the pyrolysis temperature in the muffle furnace is 400 ℃, or 500 ℃, or 600 ℃ or 700 ℃, and the pyrolysis reaction rate is 3 ℃ min-1.
4. The method according to claim 1, wherein the magnetic biochar preparation method comprises the following steps: and (2) putting the dry sludge into a quartz boat, pyrolyzing the dry sludge in a quartz tube resistance furnace under the atmosphere of N2 at the pyrolysis temperature of 400-700 ℃, keeping for 1h, cooling, taking out the quartz boat from the furnace, collecting solids, and uniformly mixing the obtained solids for later use before storing in a dryer.
5. Method according to claim 4, characterized in that the method steps are as follows: the N2 gas amount is 200 Ml/min.
6. Method according to claim 4, characterized in that the method steps are as follows: the pyrolysis temperature in the resistance furnace is 400 ℃, or 500 ℃, or 600 ℃ or 700 ℃.
7. The method according to claim 1, characterized in that the method comprises the following specific steps:
s1, preparing magnetic biochar;
s2, preparing an adsorption component, wherein the adsorption component contains the magnetic biochar and a filter screen wrapping the magnetic biochar;
s3, excavating adsorption grooves, excavating at least one adsorption groove in the heavy metal polluted soil to be repaired, and paving the adsorption component in the groove;
s4, constructing a repairing electric field which is composed of a positive electrode and a negative electrode buried in soil on two sides of the adsorption groove;
s5, hanging a spraying component, wherein the spraying component is hung above the soil on one side of the adsorption groove and comprises spray heads uniformly distributed for spraying water;
s6, spraying water, starting a spraying assembly, and gradually dissolving metal ions in the soil in water;
s7, passing the metal ions through the adsorption component arranged in the groove under the action of the electric field, and adsorbing and purifying the metal ions by the magnetic biochar;
s7, switching off the power supply, taking out the adsorption component and the positive and negative electrodes, taking out the magnetic biochar in the adsorption component, and performing centralized treatment;
s8, repeating the steps 1-7 for at least 1 time, and then detecting the heavy metal residual quantity in the soil until the heavy metal residual quantity reaches the standard.
8. The method according to claim 6, characterized in that the method comprises the following specific steps:
s21, preparing magnetic biochar;
s22, preparing an adsorption component, wherein the adsorption component contains the magnetic biochar and a filter screen wrapping the magnetic biochar;
s31, excavating the soil to be repaired, constructing an inclined bottom groove, paving a bottom plate at the bottom of the inclined bottom groove, and then backfilling the soil to be repaired;
s32, excavating at least one adsorption groove in the backfilled heavy metal polluted soil to be repaired, and paving the adsorption component in the groove;
s24, constructing a repairing electric field which is composed of a positive electrode and a negative electrode buried in soil on two sides of the adsorption groove;
s25, hanging a spraying component, wherein the spraying component is hung above the soil on one side of the adsorption groove and comprises spray heads uniformly distributed for spraying water;
s26, spraying water, starting a spraying assembly, and gradually dissolving metal ions in the soil in water;
s27, passing the metal ions through the adsorption component arranged in the groove under the action of the electric field, and adsorbing and purifying the metal ions by the magnetic biochar;
s28, switching off the power supply, taking out the adsorption component and the positive and negative electrodes, taking out the magnetic biochar in the adsorption component, and performing centralized treatment;
s29, repeating the steps 1-7 for at least 1 time, and then detecting the heavy metal residual quantity in the soil until the heavy metal residual quantity reaches the standard.
9. An apparatus for rapid electrical remediation of contaminated soil using magnetic biochar for use in the remediation method of claim 8, the apparatus comprising a first positive electrode, a first negative electrode, a first adsorption element, an adsorption trench, a spray element; the adsorption component comprises a filter frame, an adsorption bag capable of being taken out quickly is arranged in the filter frame, and the magnetic charcoal is wrapped in the adsorption bag.
10. The device as claimed in claim 9, wherein the bottom of the adsorption component is further provided with a bottom plate which is obliquely inserted into the soil, one end of the bottom plate is provided with a hanging ring, the other end of the bottom plate is provided with a backflow groove, the backflow groove is provided with a backflow pipe, the backflow pipe penetrates through the bottom plate and is connected with an external water pumping device, the backflow groove is provided with a water level meter, the water level meter is communicated with a controller through a circuit arranged in the bottom plate, the controller is connected with and controls the water pumping device through a circuit, an outlet of the water pumping device is connected with a three-way valve, and the three-way valve is communicated with the spraying component through a.
CN201911305193.0A 2019-12-17 2019-12-17 Method and device for rapidly electrically repairing heavy metal contaminated soil by using magnetic biochar Pending CN110976505A (en)

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CN111662728A (en) * 2020-07-29 2020-09-15 杨凌职业技术学院 Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof
CN111872096A (en) * 2020-06-22 2020-11-03 罗培佳 Self-extending net type heavy metal contaminated soil remediation method
CN112108118A (en) * 2020-09-21 2020-12-22 黄河水利职业技术学院 Magnetic biomass charcoal based on Fenton sludge and cellulose and preparation method and application thereof
CN113546952A (en) * 2021-06-02 2021-10-26 华南师范大学 Magnetic biochar soil remediation agent for soil heavy metal pollution and preparation method and application thereof
CN113976599A (en) * 2021-09-20 2022-01-28 昆明理工大学 In-situ pollution control method for sulfur-containing mine solid waste
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Publication number Priority date Publication date Assignee Title
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CN112108118A (en) * 2020-09-21 2020-12-22 黄河水利职业技术学院 Magnetic biomass charcoal based on Fenton sludge and cellulose and preparation method and application thereof
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CN113976599A (en) * 2021-09-20 2022-01-28 昆明理工大学 In-situ pollution control method for sulfur-containing mine solid waste

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