CN111468502B - Heavy metal polluted plant stem treatment and high-value utilization method - Google Patents
Heavy metal polluted plant stem treatment and high-value utilization method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Environmental & Geological Engineering (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of heavy metal polluted plant treatment, and particularly discloses a heavy metal polluted plant stem treatment and high-value utilization method, which comprises the steps of carrying out anaerobic fermentation on heavy metal polluted plant stems; placing the fermented plant stems in a phosphoric acid solution to obtain a mixed solution, and carrying out first-stage heat treatment on the mixed solution at the temperature of 160 ℃ under an oxygen-containing atmosphere to obtain a precursor; then carrying out second-stage heat treatment on the precursor at the temperature of 500-800 ℃ in protective atmosphere to obtain a porous carbon material, and recovering heavy metal from tail gas of the second-stage heat treatment; and filling a sulfur simple substance into the porous carbon material to prepare the lithium-sulfur battery positive active material. The method is simple to operate, can simultaneously realize the recovery of heavy metals and the high-valued utilization of harmful resources, and effectively develops a new path and a solution for the subsequent treatment of plants after the heavy metals are enriched.
Description
The technical field is as follows:
the invention belongs to the field of environmental engineering, and particularly relates to a high-value utilization method of plants enriched with heavy metals.
Background art:
because the heavy metal content in the environment is continuously increased due to various human activities and exceeds the normal range, the human health is directly harmed, the environmental quality is deteriorated, the environmental problems become more and more prominent, and the treatment of heavy metal pollution is not slow. The heavy metal pollution remediation method is mainly characterized in that heavy metal substances are thoroughly removed from a polluted water body or the migration capacity and the biological availability of heavy metals in the polluted water body are reduced, and phytoremediation of heavy metal pollution in the water body is a low-cost, green and environment-friendly remediation method.
The common treatment methods of plants enriched with heavy metals mainly include a direct incineration method, a high-temperature decomposition method, an ashing method and a liquid phase extraction method to recover the heavy metals enriched in the plants, and on one hand, the methods have poor recovery effect on the heavy metals and are easy to cause secondary pollution, and on the other hand, the plants enriched with heavy metals are treated as wastes and are not effectively utilized.
The lithium ion battery is widely researched as a novel alternative energy source, and the sulfur has the characteristics of small density, low price, environmental friendliness, high theoretical specific capacity and the like, and is considered to be an excellent lithium ion battery cathode material. Lithium-sulfur batteries are of great interest for theoretical capacities and energy densities of up to 1675mAh/g and 2600Wh/kg, but during charging and discharging, the occurrence of the polysulfide shuttling effect, the active substance sulfur and its discharge product Li2S2And Li2Poor conductivity of S and the like, and the commercial application of the lithium-sulfur battery is hindered. In view of the above problems exhibited by lithium sulfur batteries, research efforts are mainly focused on modifying a sulfur positive electrode with a nano conductive carbon material as a sulfur carrier. Namely, the carbon-sulfur composite material is prepared by compounding nano conductive carbon materials (such as carbon nano tubes, graphene, MOF materials and the like) and sulfur, so that the conductivity and the cycle reversibility of the lithium-sulfur battery are improved. However, these carbon materials have problems of complicated preparation process, high cost, difficulty in industrial scale-up production, and the like. In the experimental process, the carbon material obtained after the carbonization of the heavy metal enriched plant is found to have good conductivity and large pore volume and specific surface area, can effectively improve the electrode conductivity, relieve the problem of volume expansion in the charging and discharging process and greatly improve the electrochemical performance of the lithium-sulfur battery.
The invention content is as follows:
in order to solve the defects that the heavy metal treatment effect is limited, the resources are not effectively utilized and the like in the existing heavy metal polluted plant stem recovery, the invention provides a heavy metal polluted plant stem treatment and high-valued utilization method, and aims to improve the recovery effect of the heavy metals of the plant stems and realize the high-valued utilization of the resources.
The existing heavy metal polluted plant stalks mainly adopt a direct burning method, a high-temperature decomposition method, an ashing method and a liquid phase extraction method, and the methods also have the technical defects of unsatisfactory heavy metal treatment effect, insufficient resources, high-value utilization and the like. The invention aims to solve the problem of heavy metal pollution of plant stalks polluted by heavy metal, and through a great deal of research, the inventor finds that the recovery of the heavy metal can be effectively realized by combining anaerobic fermentation with a two-stage heat treatment process, and not only can the inventor feel that the inventor has an accident that on the basis of the process, the acid type, the treatment atmosphere and the treatment temperature of the two-stage heat treatment are further regulated and controlled, the recovery of the polluted heavy metal can be realized, meanwhile, the heavy metal can be reasonably utilized for pore forming and proper doping, and the electrode material with good electrical performance can be obtained; therefore, the following technical scheme is provided:
a heavy metal polluted plant stem treatment and high-value utilization method comprises the following steps:
step (1): carrying out anaerobic fermentation on the plant stalks polluted by the heavy metals;
step (2): placing the fermented plant stems in a phosphoric acid solution to obtain a mixed solution, and carrying out first-stage heat treatment on the mixed solution at the temperature of 160 ℃ under an oxygen-containing atmosphere to obtain a precursor;
and (3): then carrying out second-stage heat treatment on the precursor at the temperature of 500-800 ℃ in protective atmosphere to obtain a porous carbon material, and recovering heavy metal from tail gas of the second-stage heat treatment;
and (4): and filling a sulfur simple substance into the porous carbon material to prepare the lithium-sulfur battery positive active material.
According to the technical scheme, by controlling the anaerobic fermentation, the two-stage heat treatment process and the process parameters, the effective recovery of heavy metals can be realized, the lithium-sulfur battery anode material with excellent electrical properties can be co-produced, the effective treatment of heavy metal-polluted plant stalks and the high-value conversion of resources are realized, and the method has a wide market application prospect.
The method is simple and easy to operate, effectively develops a new way and a new solution for the subsequent treatment of the plants (plants polluted by heavy metals) after the heavy metals are enriched, has great significance for recycling the heavy metals, can be used for expanded production, has rich surface active functional groups and the characteristic of metal-heteroatom co-doping, can be used as an electrode material, realizes the recycling of the heavy metals and the recycling of wastes, and creates the regeneration value. The carbon-sulfur composite material prepared from the porous biochar also shows excellent electrochemical performance.
The plant stalk is at least one of rape stalk, peanut stalk and sunflower stalk.
Preferably, the heavy metal in the plant stalks is at least one of heavy metal pollution elements such as lead, cadmium, zinc, copper and the like.
The method is particularly suitable for the plant stalks with the heavy metal content higher than 20 mg/kg. The method is particularly suitable for plant straws with heavy metal content exceeding the national standard, can solve the problem of heavy metal polluted plant straw accumulation, and can regulate and control the element quantity of the prepared porous carbon, thereby producing the positive active material with excellent electrical properties at high yield.
According to the technical scheme, the plant stalks are dried in advance and then crushed into powder.
Preferably, the drying temperature of the plant stalks is 60-105 ℃, the drying time is 12-24h, and the granularity of the powder after being crushed is 100-200 meshes.
In the invention, a certain amount of heavy metal enriched plant stalk powder is put into a reaction vessel, a certain amount of yeast and a proper amount of water are added, the mixture is uniformly mixed and sealed, and anaerobic fermentation is carried out. The invention creatively carries out anaerobic fermentation on the plant stalks, so that partial organic matters can be promoted to decompose, thereby promoting the activation of the organic matters, improving the subsequent heavy metal recovery and the metal mixing amount of the carbon material, and improving the performance of the anode material.
Preferably, water and yeast are added to the plant stalk powder, followed by anaerobic fermentation under closed conditions.
The inoculation amount of the microzyme is 1-30% of the plant stalk powder; preferably 3 to 10%.
The addition amount of the water is 1-5 times of the plant stalk powder; preferably 3 to 4 times.
The temperature of anaerobic fermentation is 20-50 ℃; preferably 40-45 deg.c.
The anaerobic fermentation time is 10-24 h.
According to the invention, through the anaerobic fermentation, and further the synergistic control of the acid type, the concentration of phosphoric acid, the oxygen-containing atmosphere interface reaction of the first stage heat treatment and the heat treatment temperature, the appearance of the prepared precursor can be regulated and controlled, the microscopic active groups of the material are improved, in addition, heavy metals in plants can be bonded and passivated, the recovery efficiency of the heavy metals is ensured, and the subsequent second stage heat treatment is further facilitated to be improved to obtain the porous carbon material with excellent electrical properties.
The inventor researches and discovers that phosphoric acid can bring better effect in the system, and can contribute to improving the recovery effect of heavy metals and the electrical property of the material.
In the invention, in the step (2), the mass fraction of phosphoric acid in the phosphoric acid solution is 50-85%; even more preferably 75-85%; most preferably 85%. Researches show that the cake-shaped precursor can be obtained by adding phosphoric acid, and in addition, the method is helpful for obtaining active groups and bonding and passivating the structure of heavy metals, so that the recovery effect of the heavy metals can be further improved.
Preferably, the solid-liquid volume ratio of the fermented plant stalks to the phosphoric acid solution is 1 g: 1-5 mL.
The invention creatively carries out the first-stage heat treatment in the temperature range under the oxygen-containing atmosphere, endows the material with richer active groups through the interface action of the oxygen-containing atmosphere and the solution, improves the bonding action of the material on heavy metals, reduces the loss of the heavy metals, is not only beneficial to the second-stage heat treatment to obtain the carbon material doped with heteroatoms and metals in situ, and is beneficial to further improving the electrical properties of the subsequently prepared material.
The oxygen-containing atmosphere may be air.
The present inventors have found that, in order to further improve the heavy metal recovery effect and further improve the electrical properties of the subsequently produced positive electrode active material, it is necessary to further coordinate the heat treatment temperature with the atmosphere, the type of acid, and the concentration of acid in step (2).
Preferably, the temperature of the first-stage heat treatment is 150-160 ℃. Researches show that the recovery effect of heavy metals can be further improved in a preferred temperature range by matching with other parameters, and the performance of the subsequently prepared cathode active material can be improved.
Preferably, the treatment time of the first stage of heat treatment is 10-24 h; more preferably 12 to 15 hours.
And obtaining a precursor after the first-stage heat treatment is finished. The invention innovatively carries out the second-stage heat treatment on the carbon material, can effectively ensure the recovery of heavy metal by cooperating with the temperature control in the second-stage heat treatment process, and can fully utilize the heavy metal bonded by fermentation and the first-stage heat treatment to form a porous morphology and form a specific metal-heteroatom co-doping morphology in the carbon material, thereby effectively improving the electrical property of the material.
The second stage heat treatment is preferably carried out in a tube furnace.
The protective atmosphere may be nitrogen or an inert gas.
The flow rate of the protective atmosphere is 0.1-1L/min.
Preferably, the temperature of the second stage heat treatment is 600-700 ℃. Under the conditions of fermentation, phosphoric acid activation and passivation and first-stage heat treatment, the metal holding amount can be regulated and controlled at an optimal temperature, and the electrical property of the prepared material can be further improved.
The temperature rise rate of the second stage heat treatment is 5-20 ℃/min; preferably 10 deg.C/min.
Preferably, the time of the second stage heat treatment is 2-5 h.
In the invention, the heavy metal enriched in the plant material is recovered from the tail gas of the second stage heat treatment, so that the effective recovery of the metal elements is realized.
Preferably, acid liquor is adopted to absorb tail gas of the second stage heat treatment, and then alkali is used for precipitation, so as to recover heavy metals. For example, the tail gas of the second stage heat treatment is passed through a tail gas treatment device (nitric acid solution with pH value of 1-3) to recover heavy metals escaping from the sintering process, alkali liquor is added into the recovered solution to obtain heavy metal precipitate, and then the heavy metals are filtered and recovered.
In the present invention, after the second heat treatment, the obtained product is washed and dried to obtain the porous carbon material.
The washing treatment is preferably water washing, or acid washing followed by water washing to neutrality.
For example, the product of the second stage heat treatment is naturally cooled, taken out, dispersed in nitric acid solution with pH of 1 for 10-30min, shaken for 5-12h, washed to neutrality by deionized water, dried and sieved to obtain the porous biochar, wherein the drying temperature is 60-100 ℃, and the mesh number of the sieve is 400 meshes. The inventor researches and discovers that the electrical property of the material in the lithium-sulfur battery can be unexpectedly improved by adopting water washing or water washing after acid washing compared with alkali washing commonly adopted in the prior art.
The inventor researches and discovers that the fermentation, first-stage heat treatment and second-stage heat treatment process can effectively solve the problem of heavy metal pollution of plants and effectively recover heavy metals in the plants, and the treatment process can reasonably utilize the heavy metals to form porous morphology and control the conversion of the heavy metals through parameters, so that the prepared porous carbon material has good performance. Research shows that the porous carbon material prepared by the invention has unexpected effect on being used as a positive electrode material of a lithium-sulfur battery.
In the invention, the porous carbon material can be prepared into the lithium-sulfur battery cathode material by adopting the existing method.
Preferably, the porous carbon material and the sublimed sulfur are mixed and then placed in a closed container, and are treated at 155-160 ℃ in advance, and then are treated at 195-200 ℃ to prepare the lithium-sulfur battery positive electrode active material. Under the two-stage treatment, the performance of the prepared electrode material is further improved.
Preferably, the positive electrode active material, the conductive agent, and the binder are slurried with a solvent, combined on the surface of the positive electrode current collector, cured, sliced to obtain a positive electrode sheet, and then assembled into the lithium-sulfur battery.
The invention discloses a preferable method for high-value utilization of heavy metal enriched plants, which comprises the following steps:
(1) drying and crushing the heavy metal-enriched plant stalks into powder; putting a certain mass of heavy metal enriched plant stem powder into a reaction vessel, adding a certain amount of yeast and a proper amount of water, uniformly mixing, sealing, and carrying out anaerobic fermentation for 10-24 h. Wherein the addition amount of yeast is 3-30% of the weight of the plant stalk powder.
(2) Adding a phosphoric acid solution with a certain volume and mass fraction of 85%, placing the mixture in a forced air drying box, pre-carbonizing the mixture for 10 to 24 hours at the temperature of 150-.
(3) Then directly transferring the cake-shaped precursor into a tubular furnace, and sintering for 2-5h at the temperature of 600-700 ℃ in the nitrogen atmosphere;
(4) recovering heavy metals escaping from the sintering process by tail gas through a tail gas treatment device (with the pH value of 1-3 nitric acid solution) during sintering, and adding alkali liquor into the recovered solution to obtain heavy metal precipitate, separating and recovering the heavy metals; leaching and washing the sintered product to neutrality by using deionized water, removing heavy metal ions and other soluble impurities in the sintered product, and precipitating and separating the filtrate by adding an alkaline solution to recover the heavy metal ions; and finally, drying and sieving the residual solid product to obtain the porous biochar.
(5) Reacting the prepared biochar with sublimed sulfur by a physical melting method to obtain a carbon-sulfur composite material; and then, carrying out size mixing and smear slicing on the carbon-sulfur composite material to obtain a positive plate, and finally assembling the positive plate into a button battery in a glove box to detect the electrochemical performance of the button battery.
In the step (5), the porous carbon material and the sublimed sulfur are mixed according to the mass ratio of 3; 7, uniformly mixing, placing in a closed reaction vessel, reacting for 12h at 155 ℃, and reacting for 3h at 200 ℃ to obtain the carbon-sulfur composite material. Mixing the carbon-sulfur composite material, acetylene black and polyvinylidene fluoride according to a certain proportion, placing the mixture into a closed reaction vessel, stirring the mixture for 5 to 12 hours by taking N, N-dimethyl pyrrolidone as a solvent to prepare slurry, coating the slurry on an aluminum foil, drying the aluminum foil at the temperature of between 50 and 60 ℃, slicing the aluminum foil, and preparing the button cell in a glove box.
Advantageous effects
1. The invention provides a brand-new treatment idea of the heavy metal polluted plant stalks, and compared with the existing methods such as an incineration method, a high-temperature decomposition method, an ashing method, a liquid phase extraction method and the like, the heavy metal can be more effectively recovered.
2. According to the method, the plant stalks polluted by heavy metal are taken as a processing object, anaerobic fermentation, a first-stage heat treatment and a second-stage heat treatment process are innovatively adopted, and the characteristics of heavy metal pollution can be utilized to form a porous shape and control the doping proportion of metal and heteroatom on the premise of ensuring the good heavy metal recovery effect of the plant stalks through the cooperative control of materials and parameters in each treatment process, so that the obtained porous carbon material shows excellent electrical properties when used as a lithium-sulfur battery material, and the high-value recovery of resources is realized.
Description of the drawings:
fig. 1 is a graph showing different-rate charge and discharge curves of the carbon-sulfur composite material prepared in example 1.
Fig. 2 is a graph showing different-rate charge and discharge curves of the carbon-sulfur composite material prepared in example 2.
Fig. 3 is a graph showing different-rate charge and discharge curves of the carbon-sulfur composite material prepared in example 3.
Fig. 4 is a graph showing different-rate charge and discharge curves of the carbon-sulfur composite material prepared in comparative example 1.
Fig. 5 is a graph showing different-rate charge and discharge curves of the carbon-sulfur composite material prepared in comparative example 2.
Fig. 6 is a graph showing different-rate charge and discharge curves of the carbon-sulfur composite material prepared in comparative example 3.
The specific implementation mode is as follows:
the invention will now be further described by way of the following examples, which are not intended to limit the scope of the invention in any way. It will be understood by those skilled in the art that equivalent substitutions and corresponding modifications of the technical features of the present disclosure can be made within the scope of the present disclosure.
Example 1
Drying rape stalks with excessive lead and cadmium (the content of heavy metals is higher than 20mg/kg), crushing into powder, putting 3g rape stalk powder into a beaker, adding 0.1g yeast and 10mL water, mixing uniformly, standing for 0.5h, sealing, anaerobic fermentation is carried out for 15h at the temperature of 40 ℃, 7mL of phosphoric acid solution with the mass fraction of 85 percent is added and then the mixture is placed in a forced air drying oven, pre-carbonizing at 150 deg.C for 12h under open atmosphere to obtain cake precursor, directly transferring the cake precursor into a tube furnace, heating to 700 ℃ under the nitrogen atmosphere with the flow of 0.5L/min and the heating rate of 10 ℃/min, and sintering at the temperature for 2h, recovering heavy metal escaped from the sintering process by tail gas through a tail gas treatment device (nitric acid solution with pH value of 1) during sintering, adding alkali liquor into the recovered solution to obtain heavy metal precipitate, and filtering to recover the heavy metal; naturally cooling the sintered product, taking out the sintered product, dispersing the sintered product in a nitric acid solution with the pH value of 1, performing ultrasonic treatment for 15min, oscillating the sintered product for 12 hours, performing suction filtration and washing on the sintered product by using deionized water until the sintered product is neutral, and adding an alkaline solution into the filtrate to precipitate, separate and recover heavy metal ions; and finally, drying and sieving the residual solid product to obtain the porous biochar. Mixing porous biological carbon and sublimed sulfur according to the mass ratio of 3: 7, uniformly mixing, placing in a weighing bottle, reacting for 12h at 155 ℃, reacting for 3h at 200 ℃ to obtain a carbon-sulfur composite material, mixing the carbon-sulfur composite material, acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, placing in the weighing bottle, stirring for 5h by using N, N-dimethyl pyrrolidone as a solvent to prepare a slurry, coating on an aluminum foil, drying at 60 ℃, slicing, and preparing the button cell in a glove box.
The discharge data are shown in figure 1.
Example 2
Drying peanut stalks with excessive lead and cadmium heavy metals (the content is higher than 20mg/kg), crushing the dried peanut stalks into powder, putting 3g of peanut stalk powder into a beaker, adding 0.9g of yeast and 5mL of water, uniformly mixing, standing for 0.5h, sealing, anaerobic fermentation is carried out for 15h at the temperature of 40 ℃, 7mL of phosphoric acid solution with the mass fraction of 80 percent is added and then is placed in a forced air drying oven, pre-carbonizing at 160 deg.C for 12h under open atmosphere to obtain cake precursor, directly transferring the cake precursor into a tube furnace, heating to 600 ℃ under the nitrogen atmosphere with the flow of 0.6L/min and the heating rate of 10 ℃/min, and sintering at the temperature for 2h, recovering heavy metal escaped from the sintering process by tail gas through a tail gas treatment device (nitric acid solution with pH value of 1) during sintering, adding alkali liquor into the recovered solution to obtain heavy metal precipitate, and filtering to recover the heavy metal; naturally cooling the sintered product, taking out the sintered product, dispersing the sintered product in a nitric acid solution with the pH value of 1, performing ultrasonic treatment for 15min, oscillating the sintered product for 12 hours, performing suction filtration and washing on the sintered product by using deionized water until the sintered product is neutral, and adding an alkaline solution into the filtrate to precipitate, separate and recover heavy metal ions; and finally, drying and sieving the residual solid product to obtain the porous biochar. Mixing porous sulfur and sublimed sulfur according to the mass ratio of 3: 7, uniformly mixing, placing in a weighing bottle, reacting for 12h at 155 ℃, reacting for 3h at 200 ℃ to obtain a carbon-sulfur composite material, mixing the carbon-sulfur composite material, acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, placing in the weighing bottle, stirring for 5h by using N, N-dimethyl pyrrolidone as a solvent to prepare a slurry, coating on an aluminum foil, drying at 60 ℃, slicing, and preparing the button cell in a glove box.
The discharge data is shown in figure 2.
Example 3
Drying oil sunflower stalks with excessive lead and cadmium heavy metals (the content is higher than 20mg/kg), crushing into powder, putting 3g of oil sunflower stalk powder into a beaker, adding 0.1g of yeast and 10mL of water, uniformly mixing, standing for 0.5h, sealing, anaerobic fermentation is carried out for 15h at the temperature of 40 ℃, 7mL of phosphoric acid solution with the mass fraction of 75 percent is added and then the mixture is placed in a forced air drying oven, pre-carbonizing at 110 deg.C for 12h to obtain cake precursor, directly transferring the cake precursor into a tube furnace, heating to 800 ℃ under the nitrogen atmosphere with the flow of 0.5L/min and the heating rate of 10 ℃/min, sintering for 2 hours at the temperature, recovering heavy metal escaped in the sintering process by tail gas through a tail gas treatment device (nitric acid solution with pH value of 1) during sintering, adding alkali liquor into the recovered solution to obtain heavy metal precipitate, and filtering to recover the heavy metal; naturally cooling the sintered product, taking out the sintered product, dispersing the sintered product in a nitric acid solution with the pH value of 1, performing ultrasonic treatment for 15min, oscillating the sintered product for 12 hours, performing suction filtration and washing on the sintered product by using deionized water until the sintered product is neutral, and adding an alkaline solution into the filtrate to precipitate, separate and recover heavy metal ions; and finally, drying and sieving the residual solid product to obtain the porous biochar. Mixing porous sulfur and sublimed sulfur according to the mass ratio of 3: 7, uniformly mixing, placing in a weighing bottle, reacting for 12h at 155 ℃, reacting for 3h at 200 ℃ to obtain a carbon-sulfur composite material, mixing the carbon-sulfur composite material, acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, placing in the weighing bottle, stirring for 5h by using N, N-dimethyl pyrrolidone as a solvent to prepare a slurry, coating on an aluminum foil, drying at 60 ℃, slicing, and preparing the button cell in a glove box.
The discharge data is shown in figure 3.
Comparative example 1
Compared with the example 1, the difference is that the anaerobic fermentation treatment is not carried out, and the specific operation is as follows:
drying the rape stalks (same as the example 1) and then crushing the rape stalks into powder, putting 3g of rape stalk powder into a beaker, adding 10mL of a phosphoric acid solution with the mass fraction of 85%, then putting the mixture into an air-blast drying box, pre-carbonizing the mixture for 12 hours at 150 ℃ under an open condition to obtain a cake-shaped precursor, then directly transferring the cake-shaped precursor into a tube furnace, sintering the cake-shaped precursor for 2 hours at 700 ℃ under a nitrogen atmosphere, recovering heavy metals escaping in the sintering process by tail gas through a tail gas treatment device (a nitric acid solution with the pH value equal to 1), adding alkali liquor into the recovered solution to obtain heavy metal precipitates, and filtering and recovering the heavy metals; naturally cooling the sintered product, taking out the sintered product, dispersing the sintered product in a nitric acid solution with the pH value of 1, performing ultrasonic treatment for 15min, oscillating the sintered product for 12 hours, performing suction filtration and washing on the sintered product by using deionized water until the sintered product is neutral, and adding an alkaline solution into the filtrate to precipitate, separate and recover heavy metal ions; and finally, drying and sieving the residual solid product to obtain the porous biochar. Mixing porous sulfur and sublimed sulfur according to the mass ratio of 3: 7, uniformly mixing, placing in a weighing bottle, reacting for 12h at 155 ℃, reacting for 3h at 200 ℃ to obtain a carbon-sulfur composite material, mixing the carbon-sulfur composite material, acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, placing in the weighing bottle, stirring for 5h by using N, N-dimethyl pyrrolidone as a solvent to prepare a slurry, coating on an aluminum foil, drying at 60 ℃, slicing, and preparing the button cell in a glove box.
The discharge data is shown in figure 4.
Comparative example 2
Compared with the example 1, the difference is that no phosphoric acid is added in the first stage of heat treatment, and the specific steps are as follows:
drying and crushing rape stalks (same as example 1) enriched with heavy metals of lead and cadmium into powder, putting 3g of rape stalk powder into a beaker, adding 0.1g of yeast and 10mL of water, uniformly mixing, standing for 0.5h, sealing, carrying out anaerobic fermentation for 15h at 40 ℃, putting the mixture into a blast drying box, pre-carbonizing for 12h at 150 ℃ under an open condition to obtain a cake-shaped precursor, directly transferring the cake-shaped precursor into a tubular furnace, sintering for 2h at 700 ℃ under a nitrogen atmosphere, recovering heavy metals escaping in the sintering process from tail gas through a tail gas treatment device (nitric acid solution with pH equal to 1) during sintering, adding alkali liquor into the recovered solution to obtain heavy metal precipitate, and filtering and recovering the heavy metals; naturally cooling the sintered product, taking out the sintered product, dispersing the sintered product in a nitric acid solution with the pH value of 1, performing ultrasonic treatment for 15min, oscillating the sintered product for 12 hours, performing suction filtration and washing on the sintered product by using deionized water until the sintered product is neutral, and adding an alkaline solution into the filtrate to precipitate, separate and recover heavy metal ions; and finally, drying and sieving the residual solid product to obtain the porous biochar. Mixing porous sulfur and sublimed sulfur according to the mass ratio of 3: 7, uniformly mixing, placing in a weighing bottle, reacting for 12h at 155 ℃, reacting for 3h at 200 ℃ to obtain a carbon-sulfur composite material, mixing the carbon-sulfur composite material, acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, placing in the weighing bottle, stirring for 5h by using N, N-dimethyl pyrrolidone as a solvent to prepare a slurry, coating on an aluminum foil, drying at 60 ℃, slicing, and preparing the button cell in a glove box. The discharge data is shown in figure 5.
Comparative example 3
Compared with the example 1, the difference is only that the second stage heat treatment is alkali activation roasting, which is specifically as follows:
drying and crushing rape stalks (same as example 1) enriched with lead and cadmium heavy metals into powder, putting 3g of rape stalk powder into a beaker, adding 10mL of phosphoric acid solution with the mass fraction of 85%, putting the mixture into an air-blast drying box, pre-carbonizing the mixture for 12 hours at 150 ℃ under the condition of opening to obtain a cake-shaped precursor, naturally cooling the cake-shaped precursor, washing the cake-shaped precursor to be neutral with water, carrying out suction filtration and drying, mixing and grinding the carbon precursor and an alkaline activator KOH according to a ratio of 2:1, transferring the mixture into a tubular furnace, sintering the mixture for 2 hours at 700 ℃ under the nitrogen atmosphere, recovering the heavy metals escaping in the sintering process from tail gas through a tail gas treatment device (the pH is 1 nitric acid solution), adding alkali liquor into the recovered solution to obtain heavy metal precipitate, and filtering and recovering the heavy metals; naturally cooling the sintered product, taking out the sintered product, dispersing the sintered product in a nitric acid solution with the pH value of 1 for ultrasonic treatment for 15min, oscillating the sintered product for 12 hours, then performing suction filtration and washing on the sintered product by using deionized water until the sintered product is neutral, removing heavy metal ions and other soluble impurities in the sintered product, and adding an alkaline solution into filtrate for precipitation separation and recovery of the heavy metal ions; and finally, drying and sieving the residual solid product to obtain the porous biochar. Mixing the porous sulfur with the sublimed sulfur according to the mass ratio of 3; 7, uniformly mixing, placing in a weighing bottle, reacting for 12h at 155 ℃, reacting for 3h at 200 ℃ to obtain a carbon-sulfur composite material, mixing the carbon-sulfur composite material, acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, placing in the weighing bottle, stirring for 5h by using N, N-dimethyl pyrrolidone as a solvent to prepare a slurry, coating on an aluminum foil, drying at 60 ℃, slicing, and preparing the button cell in a glove box.
The discharge data is shown in figure 6.
Comparative example 4:
the difference compared to example 1 is that boric acid was used instead of the phosphoric acid, the other parameters being unchanged.
Comparative example 5:
compared with example 1, the difference is that the temperature of the first stage heat treatment is 200 ℃.
Comparative example 6:
compared with example 1, the difference is that in the first stage heat treatment, the amount of phosphoric acid used is 30%.
The test results of each example and comparative example are shown in table 1.
TABLE 1
As can be seen from table 1, by the method of the present invention, through the anaerobic fermentation, the two-stage heat treatment process and the control of process parameters, not only can effective recovery of heavy metals be achieved, but also lithium sulfur battery cathode materials with excellent electrical properties can be co-produced, and effective treatment of heavy metal-contaminated plant stalks and high value conversion of resources are achieved.
Further research shows that under the anaerobic fermentation condition, phosphoric acid is used as an activating agent and a metal passivator, and the concentration of the phosphoric acid is controlled to be 50-85%; preferably 80 to 85%, particularly 85%. The temperature of the first stage of heat treatment in the treatment process is controlled to be 150-160 ℃; and the temperature of the second stage of heat treatment is controlled to be 600-700 ℃, so that the doping amount of heavy metal in the carbon material can be regulated, the battery material with better performance can be obtained, and in addition, the recovery rate of the metal can be ensured.
Claims (10)
1. A heavy metal polluted plant stem treatment and high-value utilization method is characterized by comprising the following steps:
step (1): drying and crushing the plant stalks polluted by the heavy metal into powder; adding water and inoculating yeast into the plant stalk powder, and performing anaerobic fermentation under a closed condition; the heavy metal in the plant stalks is at least one of lead, cadmium, zinc and copper;
step (2): placing the fermented plant stems in a phosphoric acid solution to obtain a mixed solution, and carrying out first-stage heat treatment on the mixed solution at the temperature of 160 ℃ in an oxygen-containing atmosphere to obtain a precursor; in the phosphoric acid solution, the mass fraction of phosphoric acid is 50-85%;
and (3): then carrying out second-stage heat treatment on the precursor in a protective atmosphere at the temperature of 500-800 ℃, washing and drying the obtained product to obtain a porous carbon material, and recovering heavy metal from tail gas of the second-stage heat treatment;
and (4): and filling a sulfur simple substance into the porous carbon material to prepare the lithium-sulfur battery positive active material.
2. The method for treating and utilizing heavy metal-contaminated plant stalks according to claim 1, wherein the heavy metal content of said plant stalks is higher than 20 mg/kg.
3. The method for treating and highly utilizing heavy metal-contaminated plant stalks according to claim 1, wherein the inoculation amount of said yeast is 1 to 30% of the plant stalk powder;
the addition amount of the water is 1-5 times of the plant stalk powder.
4. The method for treating and utilizing heavy metal-contaminated plant stalks according to claim 3, wherein the temperature of anaerobic fermentation is 20 to 50 ℃;
the anaerobic fermentation time is 10-24 h.
5. The method for treating and utilizing heavy metal-contaminated plant stalks according to claim 1, wherein in the step (2), the mass fraction of phosphoric acid in the phosphoric acid solution is 75 to 85%.
6. The heavy metal-contaminated plant stem treatment and high-value utilization method according to claim 1, wherein the solid-liquid volume ratio of the fermented plant stems to the phosphoric acid solution is 1 g: 1-5 mL.
7. The method for treating and utilizing heavy metal-contaminated plant stalks according to claim 1, wherein the heavy metal is recovered by absorbing the tail gas of the second stage of heat treatment with an acid solution and then precipitating with an alkali.
8. The method for treating and utilizing heavy metal-contaminated plant stalks according to claim 1, wherein the washing step is water washing or acid washing followed by water washing to neutrality.
9. The method for treating and utilizing heavy metal-contaminated plant stalks according to claim 1, wherein the porous carbon material is mixed with sublimed sulfur and then placed in a closed container, and the mixture is treated at 155-160 ℃ in advance and then at 195-200 ℃ to prepare the positive electrode active material for the lithium-sulfur battery.
10. The method for treating and utilizing heavy metal-contaminated plant stalks according to claim 1, wherein the positive electrode active material, the conductive agent and the binder are slurried with a solvent, compounded on the surface of the positive electrode current collector, cured and sliced to obtain a positive electrode sheet, and then assembled into the lithium-sulfur battery.
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