CN107321312A - Method for preparing magnetic adsorbent by using waste zinc-manganese battery and biomass - Google Patents
Method for preparing magnetic adsorbent by using waste zinc-manganese battery and biomass Download PDFInfo
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Abstract
The invention discloses a method for preparing a magnetic adsorbent by using waste zinc-manganese batteries and biomass, which is characterized by comprising the steps of pretreating electrode materials of the waste zinc-manganese batteries to prepare a biological leaching solution, then carrying out indirect biological leaching, and finally carrying out hydrothermal carbonization and synthesis to obtain the magnetic adsorbent. Manganese-zinc metal in the waste zinc-manganese battery is extracted by using sulfur oxidizing bacteria and ferrous oxidizing bacteria filtrate, so that the raw materials are easy to obtain, simple, efficient and environment-friendly; the waste zinc-manganese battery and the biomass are converted into the biological activated carbon with the magnetic adsorption performance, so that the high-added-value resource utilization of the waste battery and the waste biomass can be realized.
Description
Technical Field
The invention belongs to the technical field of adsorbent preparation, and relates to a method for preparing a magnetic adsorbent by using waste zinc-manganese batteries and biomass.
Background
The waste zinc-manganese batteries contain about 12-28% of zinc and 26-45% of manganese, and according to the statistics of the Chinese Battery Enterprise Association, the number of zinc-manganese batteries consumed in 2013 in China is up to 318 hundred million, and the zinc-manganese elements in the batteries mainly comprise ZnMn 2 O 4 、Mn 2 O 3 、Mn 3 O 4 And MnO 2 And the substances are mixed in the electrode material and are difficult to separate. The traditional hydrometallurgical zinc and manganese recovery methods, such as electrodeposition, extraction, sequential precipitation and the like, require higher process conditions and higher cost.
In recent years, scholars at home and abroad use strong acid to leach zinc and manganese ions in waste zinc-manganese batteries, and then the leaching solution is used as a precursor to successfully prepare the manganese-zinc ferrite soft magnetic material with higher added value. However, the wet leaching process using strong acid as main working medium has high requirements on equipment materials and safety. In the wet preparation method of the soft magnetic material, the chemical coprecipitation method is simple and easy to implement, but the powder agglomeration of the finished product is difficult to overcome; the sol-gel and self-propagating high-temperature synthesized products have uniform particles, small particle size, large specific surface area and stronger activity, but have higher manufacturing cost and process requirements. In addition, the existing soft magnetic material is not used as an adsorbent in sewage treatment.
Disclosure of Invention
The invention aims to provide a method for preparing a magnetic adsorbent by using waste zinc-manganese batteries and biomass, which can obtain an adsorbent with excellent adsorption performance and separation effect.
The technical scheme adopted by the invention is that the method for preparing the magnetic adsorbent by using the waste zinc-manganese batteries and the biomass comprises the steps of pretreating electrode materials of the waste zinc-manganese batteries, preparing biological leaching liquor, carrying out indirect biological leaching, and finally carrying out hydrothermal carbonization and synthesis to obtain the magnetic adsorbent.
A method for preparing a magnetic adsorbent by using waste zinc-manganese batteries and biomass specifically comprises the following steps:
step 1, taking electrode materials of waste zinc-manganese batteries, grinding the electrode materials, and screening the ground electrode materials through a screen to obtain electrode powder;
step 2, taking sulfur powder and ferrous sulfate as a mixed energy substrate, mixing thiobacillus thiooxidans liquid, leptospirillum ferrooxidans liquid and thiobacillus thiooxidans liquid to form a mixed leaching strain, regularly inoculating and culturing the mixed leaching strain in a shaking table at constant temperature by using the mixed energy substrate and nutrient salt, and removing the strain through centrifugation and filtration in sequence to obtain a biological leaching solution;
step 3, leaching the electrode powder obtained in the step 1 by using the biological leaching solution obtained in the step 2 to obtain a leaching solution, measuring the concentrations of Zn ions, mn ions and Fe ions in the leaching solution, and supplementing zinc sulfate, manganese sulfate or ferric sulfate into the leaching solution to obtain Mn 1-x Zn x Fe 2 O 4 Preparing liquid for magnetic materials;
step 4, obtaining Mn through the step 3 1-x Zn x Fe 2 O 4 Adding biomass into the magnetic material preparation liquid to obtain a mixed liquid A, gradually heating the mixed liquid to 30-60 ℃, dropwise adding a NaOH solution in the heating process to enable the pH value of the mixed liquid A to reach 10-13, then heating the mixed liquid A to 60-90 ℃, stirring to enable the mixed liquid A to be thick paste, transferring the mixed liquid A into a high-pressure reaction tank for reaction to obtain a mixed liquid B, and sequentially washing, centrifuging, drying and grinding the mixed liquid B to obtain the biomass magnetic adsorbent.
The invention is also characterized in that:
in step 1, the particle size of the electrode powder is less than 125 μm.
The solvent of the nutrient salt is water, and the solute of the nutrient salt is: (NH) in an amount of 1.0 to 3.0g/L 4 ) 2 SO 4 KH with the content of 1.0-2.0 g/L 2 PO 4 MgSO 1.0-2.0 g/L MgSO 4 ·7H 2 O and CaCl with the content of 0.25-0.5 g/L 2 ；
The solvent of the mixed energy substrate is water, the content of sulfur powder is 5-15 g/L, and the content of ferrous sulfate is 10-30 g/L.
In the inoculation and cultivation process of the step 2: the rotating speed of the shaking table is 120 r/min-160 r/min, the temperature is 30-40 ℃, and the cultivation days are 3-5 days.
In the leaching process in the step 3, the rotating speed of the shaking table is 120 r/min-160 r/min, and the leaching time is 1 h-2 h.
In the step 3: mn (Mn) 1-x Zn x Fe 2 O 4 In the magnetic material preparation liquid, the sum of the concentrations of Zn ions, mn ions and Fe ions is 1mol/L to 2mol/L, and x is 0.2 to 0.6.
In the step 4: the biomass is one of sawdust, peanut shell powder, corn straw, dried leaves, peach kernel powder and apricot kernel powder.
The mass ratio of the electrode powder to the biomass is 1:1-3.
In the step 4: the mass fraction of the NaOH solution is 10-30%, and the stirring time is 1.0-3.0 h; the reaction temperature in the high-pressure reaction tank is 180-220 ℃, and the reaction time is 5-12 h.
The invention has the beneficial effects that:
(1) According to the preparation method, manganese-zinc metal in the waste zinc-manganese battery is extracted by using sulfur oxidizing bacteria and ferrous oxidizing bacteria filtrate, so that the raw materials are easy to obtain, simple, efficient, green and environment-friendly;
(2) According to the preparation method, the waste zinc-manganese batteries and the biomass are converted into the biological activated carbon with the magnetic adsorption performance, so that high value-added resource utilization of the waste batteries and the waste biomass can be realized;
(3) The preparation method can obtain the excellent adsorbent for adsorbing the heavy metal ions in the sewage.
Drawings
FIG. 1 is a BET surface adsorption-desorption and pore size determination chart of the magnetic adsorbent obtained by the preparation method of the present invention;
FIG. 2 is an SEM image of a magnetic adsorbent obtained by the preparation method of the invention;
FIG. 3 isNi obtained by the preparation method of the invention under different adsorption temperatures 2+ The adsorption performance of (1).
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a method for preparing a magnetic adsorbent by using waste zinc-manganese batteries and biomass.
A method for preparing a magnetic adsorbent by using waste zinc-manganese batteries and biomass specifically comprises the following steps:
step 1, taking electrode materials of waste zinc-manganese batteries, grinding the electrode materials of the batteries into powder, and screening the powder by using a screen to obtain electrode powder with the particle size of less than 125 microns;
step 2, taking sulfur powder and ferrous sulfate as a mixed energy substrate, mixing thiobacillus thiooxidans liquid, leptospirillum ferrooxidans liquid and thiobacillus ferrooxidans liquid in a volume ratio of 1-2;
during the inoculation and cultivation process:
the solvent of the nutrient salt is water, and the solute of the nutrient salt is: (NH) in an amount of 1.0 to 3.0g/L 4 ) 2 SO 4 KH with the content of 1.0-2.0 g/L 2 PO 4 MgSO 1.0-2.0 g/L MgSO 4 ·7H 2 O and CaCl with the content of 0.25-0.5 g/L 2 ；
The solvent of the mixed energy substrate is water, the content of sulfur powder is 5-15 g/L, and the content of ferrous sulfate is 10-30 g/L;
the rotating speed of the shaking table is 120 r/min-160 r/min, the temperature is 30-40 ℃, and the cultivation days are 3-5 days.
Step 3, leaching the electrode powder obtained in the step 1 by using the biological leaching solution obtained in the step 2 to obtain a leaching solution, measuring the concentrations of Zn ions, mn ions and Fe ions in the leaching solution, and supplementing zinc sulfate, manganese sulfate or ferric sulfate into the leaching solution to obtain Mn 1-x Zn x Fe 2 O 4 Preparing liquid for magnetic materials;
in the leaching process: the rotating speed of the shaking table is 120 r/min-160 r/min, and the leaching time is 1 h-2 h;
Mn 1-x Zn x Fe 2 O 4 in the magnetic material preparation liquid, the sum of the concentrations of Zn ions, mn ions and Fe ions is 1mol/L to 2mol/L, and x is 0.2 to 0.6.
Step 4, obtaining Mn through the step 3 1-x Zn x Fe 2 O 4 Adding biomass into a magnetic material preparation solution to obtain a mixed solution A, gradually heating the mixed solution to 30-60 ℃, dropwise adding a NaOH solution with the mass fraction of 10-30% in the heating process to enable the pH value of the mixed solution A to reach 10-13, then heating the mixed solution A to 60-90 ℃, stirring for 1.0-3.0 h to enable the mixed solution A to be in a thick paste shape, transferring the mixed solution A into a high-pressure reaction tank for reaction to obtain a mixed solution B, and sequentially washing, centrifuging, drying and grinding the mixed solution B to obtain a biomass magnetic adsorbent;
the reaction temperature in the high-pressure reaction tank is 180-220 ℃, and the reaction time is 5-12 h;
the biomass is one of wood chips, peanut shell powder, corn straws, dried leaves, peach kernel powder and apricot kernel powder;
the mass ratio of the electrode powder to the biomass is 1:1-3.
Example 1
Step 1, taking electrode materials of waste zinc-manganese batteries, grinding the electrode materials of the batteries into powder, and screening the powder by using a screen to obtain electrode powder with the particle size of less than 125 microns;
step 2, taking sulfur powder and ferrous sulfate as a mixed energy substrate, mixing the thiobacillus thiooxidans liquid, the spirochete ferrous oxide leptospirillum liquid and the thiobacillus thiooxidans liquid which are mixed in a volume ratio of 1;
during the inoculation and cultivation process:
the solvent of the nutrient salt is water, and the solute of the nutrient salt is: (NH) in an amount of 2.0g/L 4 ) 2 SO 4 KH with the content of 1.0g/L 2 PO 4 MgSO 1.0g/L MgSO 4 ·7H 2 O and CaCl with the content of 0.25g/L 2 ；
The solvent of the mixed energy substrate is water, the content of sulfur powder is 10g/L, and the content of ferrous sulfate is 10g/L.
Step 3, leaching the electrode powder obtained in the step 1 by using the biological leaching solution obtained in the step 2 to obtain a leaching solution, measuring the concentrations of Zn ions, mn ions and Fe ions in the leaching solution, and supplementing zinc sulfate, manganese sulfate or ferric sulfate into the leaching solution to obtain Mn 1-x Zn x Fe 2 O 4 Preparing liquid for magnetic materials;
in the leaching process: the rotating speed of the shaking table is 160r/min, and the leaching time is 2h;
in the magnetic material preparation solution, the total concentration of Zn ions, mn ions and Fe ions is 2mol/L, x is 0.4, and the magnetic material preparation solution is Mn 0.6 Zn 0.4 Fe 2 O 4 。
Step 4, obtaining Mn through the step 3 0.6 Zn 0.4 Fe 2 O 4 Adding 15g of wood chips into a magnetic material preparation liquid to obtain a mixed liquid A, gradually heating the mixed liquid to 60 ℃, dropwise adding a NaOH solution with the mass fraction of 10% in the heating process to enable the pH value of the mixed liquid A to reach 10, then heating the mixed liquid A to 90 ℃, stirring for 1.0h to enable the mixed liquid A to be in a thick paste state, transferring the mixed liquid A into a high-pressure reaction tank with the temperature of 180 ℃ to react for 6h to obtain a mixed liquid B, and sequentially washing, centrifuging and drying the mixed liquid B to obtain a mixed liquid BAnd grinding to obtain the magnetic adsorbent.
As shown in fig. 1, the isotherm of the magnetic adsorbent obtained by the preparation method of the present invention belongs to an H4 type hysteresis loop in IUPAC classification, which is a typical adsorption behavior of mesoporous materials, and indicates that the magnetic adsorbent is a solid containing narrow slit-shaped pores, and the pore diameter is mostly concentrated in the range of 10nm to 30nm. Calculated by a BET equation and a BJH method, the specific surface area of the magnetic adsorbent prepared by the invention is 537.7m 2 (g) total pore volume of 0.451cm 3 G, pore volume 0.012cm 3 The/g, the average aperture is 25nm, and the pore structure of the specification has better adsorption effect on macromolecular pollutants.
Example 2
Step 1, taking electrode materials of waste zinc-manganese batteries, grinding the electrode materials of the batteries into powder, and screening the powder by using a screen to obtain electrode powder with the particle size of less than 125 microns;
step 2, taking sulfur powder and ferrous sulfate as a mixed energy substrate, mixing a thiobacillus thiooxidans liquid, a leptospirillum ferrooxidans liquid and a thiobacillus thiooxidans liquid which are mixed in a volume ratio of 1;
during the inoculation and cultivation process:
the solvent of the nutrient salt is water, and the solute of the nutrient salt is: (NH) in an amount of 2.0g/L 4 ) 2 SO 4 KH with the content of 1.0g/L 2 PO 4 MgSO 1.0g/L MgSO 4 ·7H 2 O and CaCl with the content of 0.25g/L 2 ；
The solvent of the mixed energy substrate is water, the content of sulfur powder is 8g/L, and the content of ferrous sulfate is 15g/L.
Step 3, leaching the electrode powder obtained in the step 1 by using the biological leaching solution obtained in the step 2 to obtain a leaching solution, and measuring Zn ions, mn ions and Zn ions in the leaching solutionAdding zinc sulfate, manganese sulfate or ferric sulfate into the leaching solution to obtain Mn 1-x Zn x Fe 2 O 4 Preparing liquid for magnetic materials;
in the leaching process: the rotating speed of the shaking table is 150r/min, and the leaching time is 1h;
in the magnetic material preparation solution, the total concentration of Zn ions, mn ions and Fe ions is 1mol/L, x is 0.6, and the magnetic material preparation solution is Mn 0.4 Zn 0.6 Fe 2 O 4 。
Step 4, obtaining Mn through the step 3 0.4 Zn 0.6 Fe 2 O 4 Adding 10g of peanut shell powder into a magnetic material preparation solution to obtain a mixed solution A, gradually heating the mixed solution to 50 ℃, dropwise adding a NaOH solution with the mass fraction of 10% in the heating process to enable the pH value of the mixed solution A to reach 11, then heating the mixed solution A to 80 ℃, stirring for 1.5 hours to enable the mixed solution A to be in a thick paste shape, transferring the mixed solution A into a high-pressure reaction tank with the temperature of 200 ℃ to react for 5 hours to obtain a mixed solution B, and sequentially washing, centrifuging, drying and grinding the mixed solution B to obtain the magnetic adsorbent.
As shown in figure 2, the magnetic adsorbent obtained by the preparation method has a rough surface, a large number of irregular and developed porous structures in a slit shape, and a typical structure of the surface of commercial activated carbon, and shows that the magnetic adsorbent has a high internal specific surface area and excellent adsorption performance.
Example 3
Step 1, taking electrode materials of waste zinc-manganese batteries, grinding the electrode materials of the batteries into powder, and screening the powder by using a screen to obtain electrode powder with the particle size of less than 125 microns;
step 2, taking sulfur powder and ferrous sulfate as a mixed energy substrate, mixing a thiobacillus thiooxidans liquid, a leptospirillum ferrooxidans liquid and a thiobacillus thiooxidans liquid which are mixed in a volume ratio of 1;
during the inoculation and cultivation process:
the solvent of the nutrient salt is water, and the solute of the nutrient salt is: (NH) in an amount of 1.0g/L 4 ) 2 SO 4 KH with the content of 1.0g/L 2 PO 4 MgSO 1.0g/L MgSO 4 ·7H 2 O and CaCl with the content of 0.25g/L 2 ；
The solvent of the mixed energy substrate is water, the content of sulfur powder is 10g/L, and the content of ferrous sulfate is 10g/L.
Step 3, leaching the electrode powder obtained in the step 1 by using the biological leaching solution obtained in the step 2 to obtain a leaching solution, measuring the concentrations of Zn ions, mn ions and Fe ions in the leaching solution, and supplementing zinc sulfate, manganese sulfate or ferric sulfate into the leaching solution to obtain Mn 1-x Zn x Fe 2 O 4 Preparing liquid for magnetic materials;
in the leaching process: the rotating speed of the shaking table is 160r/min, and the leaching time is 2h;
in the magnetic material preparation solution, the total concentration of Zn ions, mn ions and Fe ions is 2mol/L, x is 0.5, and the magnetic material preparation solution is Mn 0.5 Zn 0.5 Fe 2 O 4 。
Step 4, obtaining Mn through the step 3 0.5 Zn 0.5 Fe 2 O 4 Adding 15g of corncob powder into the magnetic material preparation liquid to obtain a mixed liquid A, gradually heating the mixed liquid to 60 ℃, dropwise adding a NaOH solution with the mass fraction of 15% in the heating process to enable the pH value of the mixed liquid A to reach 13, then heating the mixed liquid A to 90 ℃, stirring for 2.0h to enable the mixed liquid A to be in a thick paste shape, transferring the mixed liquid A into a high-pressure reaction tank with the temperature of 200 ℃ to react for 5h to obtain a mixed liquid B, and sequentially washing, centrifuging, drying and grinding the mixed liquid B to obtain the magnetic adsorbent.
Example 4
Step 1, taking electrode materials of waste zinc-manganese batteries, grinding the electrode materials of the batteries into powder, and screening the powder by using a screen to obtain electrode powder with the particle size of less than 125 microns;
step 2, taking sulfur powder and ferrous sulfate as a mixed energy substrate, mixing a thiobacillus thiooxidans liquid, a leptospirillum ferrooxidans liquid and a thiobacillus thiooxidans liquid which are mixed in a volume ratio of 1;
during the inoculation and cultivation process:
the solvent of the nutrient salt is water, and the solute of the nutrient salt is: (NH) in an amount of 1.0g/L 4 ) 2 SO 4 KH with the content of 1.0g/L 2 PO 4 MgSO 1.0g/L MgSO 4 ·7H 2 O and CaCl with the content of 0.25g/L 2 ；
The solvent of the mixed energy substrate is water, the content of sulfur powder is 15g/L, and the content of ferrous sulfate is 20g/L.
Step 3, leaching the electrode powder obtained in the step 1 by using the biological leaching solution obtained in the step 2 to obtain a leaching solution, measuring the concentrations of Zn ions, mn ions and Fe ions in the leaching solution, and supplementing zinc sulfate, manganese sulfate or ferric sulfate into the leaching solution to obtain Mn 1-x Zn x Fe 2 O 4 Preparing liquid for magnetic materials;
in the leaching process: the rotating speed of the shaking table is 130r/min, and the leaching time is 2h;
in the magnetic material preparation solution, the total concentration of Zn ions, mn ions and Fe ions is 2mol/L, x is 0.4, and the magnetic material preparation solution is Mn 0.4 Zn 0.6 Fe 2 O 4 。
Step 4, obtaining Mn through the step 3 0.4 Zn 0.6 Fe 2 O 4 Adding 10g of withered leaf powder into the magnetic material preparation liquid to obtain a mixed liquid A, gradually heating the mixed liquid to 50 ℃, and dropwise adding a NaOH solution with the mass fraction of 20% in the heating process to enable the pH value of the mixed liquid A to reach 11And then raising the temperature of the mixed solution A to 90 ℃, stirring for 1.0 hour to enable the mixed solution A to be in a thick paste state, transferring the mixed solution A into a high-pressure reaction tank with the temperature of 200 ℃ to react for 8 hours to obtain a mixed solution B, and sequentially washing, centrifuging, drying and grinding the mixed solution B to obtain the magnetic adsorbent.
Example 5
Step 1, taking electrode materials of waste zinc-manganese batteries, grinding the electrode materials of the batteries into powder, and screening the powder by using a screen to obtain electrode powder with the particle size of less than 125 microns;
step 2, taking sulfur powder and ferrous sulfate as a mixed energy substrate, mixing a thiobacillus thiooxidans liquid, a leptospirillum ferrooxidans liquid and a thiobacillus thiooxidans liquid which are mixed in a volume ratio of 1;
during the inoculation and cultivation process:
the solvent of the nutrient salt is water, and the solute of the nutrient salt is: (NH) in an amount of 1.0g/L 4 ) 2 SO 4 KH with the content of 1.0g/L 2 PO 4 MgSO 1.0g/L 4 ·7H 2 O and CaCl with the content of 0.25g/L 2 ；
The solvent of the mixed energy substrate is water, the content of sulfur powder is 8g/L, and the content of ferrous sulfate is 15g/L.
Step 3, leaching the electrode powder obtained in the step 1 by using the biological leaching solution obtained in the step 2 to obtain a leaching solution, measuring the concentrations of Zn ions, mn ions and Fe ions in the leaching solution, and supplementing zinc sulfate, manganese sulfate or ferric sulfate into the leaching solution to obtain Mn 1-x Zn x Fe 2 O 4 Preparing liquid for magnetic materials;
in the leaching process: the rotating speed of the shaking table is 160r/min, and the leaching time is 2h;
magnetic material preparation liquidWherein the total concentration of Zn ion, mn ion and Fe ion is 1mol/L, x is 0.5, and the magnetic material preparation solution is Mn 0.5 Zn 0.5 Fe 2 O 4 。
Step 4, obtaining Mn through the step 3 0.5 Zn 0.5 Fe 2 O 4 Adding 15g of walnut shell powder into a magnetic material preparation liquid to obtain a mixed liquid A, gradually heating the mixed liquid A to 60 ℃, dropwise adding a NaOH solution with the mass fraction of 10% in the heating process to enable the pH value of the mixed liquid A to reach 12, then heating the mixed liquid A to 90 ℃, stirring for 1.0h to enable the mixed liquid A to be in a thick paste shape, transferring the mixed liquid A into a high-pressure reaction tank with the temperature of 200 ℃ to react for 6h to obtain a mixed liquid B, and sequentially washing, centrifuging, drying and grinding the mixed liquid B to obtain the magnetic adsorbent.
The following tests were carried out on the magnetic adsorbent obtained by the preparation method of the present invention:
pre-prepared Ni 2+ 100mL of wastewater with the concentration of 100mg/L is placed in a 250mL conical flask, 1mol/L of HCl and 5% of NaOH solution are used for adjusting the wastewater to be neutral, then 0.1g of magnetic adsorbent is added into the wastewater, the conical flask is placed in a water bath oscillator with the speed of 160r/min, the sampling test is carried out at regular time, the taken sample is subjected to centrifugal separation, and then Ni is measured by a flame atomic spectrophotometer 2+ The concentration changes. The results showed that the adsorption amount of the magnetic adsorbent increased significantly with the increase in temperature, and the adsorption efficiency of the magnetic adsorbent was as high as 95% at a temperature of 50 ℃ in the water bath oscillator, as shown in fig. 3.
The magnetic adsorbent obtained by the preparation method of the invention is detected by XRD, and the characteristic peaks of C and manganese zinc ferrite can be seen from the test result, thus proving that the magnetic adsorbent contains Mn 1-x Zn x Fe 2 O 4 。
Through the mode, the preparation method disclosed by the invention has the advantages of easily available raw materials, simplicity in operation, environmental friendliness and no pollution; the magnetic adsorbent obtained by the preparation method has a measured value of isoelectric point of 7.35, and the magnetic adsorbent is electrically neutral; the magnetic adsorbent obtained by the preparation method of the invention hasThe magnetic material has excellent magnetism, the cation adsorption capacity (CEC) is 243.5mmol/100g, the magnetic material can quickly adsorb heavy metal ions in sewage, the maximum saturation magnetization is 41.6emu/g, the solid-liquid magnetic separation time after adsorption saturation is only 4-6 s, and Ni is obtained by 5 times of cyclic adsorption and desorption experiments 2+ The removal rate is maintained above 80%.
Claims (10)
1. A method for preparing a magnetic adsorbent by using waste zinc-manganese batteries and biomass is characterized in that electrode materials of the waste zinc-manganese batteries are pretreated to prepare a biological leaching solution, then indirect biological leaching is carried out, and finally hydrothermal carbonization and synthesis are carried out to obtain the magnetic adsorbent.
2. The method for preparing the magnetic adsorbent by using the waste zinc-manganese battery and the biomass as claimed in claim 1, which comprises the following steps:
step 1, taking electrode materials of waste zinc-manganese batteries, grinding the electrode materials, and screening the ground electrode materials through a screen to obtain electrode powder;
step 2, taking sulfur powder and ferrous sulfate as a mixed energy substrate, mixing thiobacillus thiooxidans liquid, leptospirillum ferrooxidans liquid and thiobacillus thiooxidans liquid to form a mixed leaching strain, regularly inoculating and culturing the mixed leaching strain in a shaking table at constant temperature by using the mixed energy substrate and nutrient salt, and removing the strain through centrifugation and filtration in sequence to obtain a biological leaching solution;
step 3, leaching the electrode powder obtained in the step 1 by using the biological leaching solution obtained in the step 2 to obtain a leaching solution, measuring the concentrations of Zn ions, mn ions and Fe ions in the leaching solution, and supplementing zinc sulfate, manganese sulfate or ferric sulfate into the leaching solution to obtain Mn 1-x Zn x Fe 2 O 4 Preparing liquid for magnetic materials;
step 4, obtaining Mn through the step 3 1-x Zn x Fe 2 O 4 Adding biomass into the magnetic material preparation solution to obtain a mixed solution A, gradually heating the mixed solution to 30-60 ℃, and dropwise adding a NaOH solution in the heating process to mixAnd (3) when the pH value of the liquid A reaches 10-13, raising the temperature of the mixed liquid A to 60-90 ℃, stirring to enable the mixed liquid A to be in a thick paste state, transferring the mixed liquid A into a high-pressure reaction tank for reaction to obtain a mixed liquid B, and sequentially washing, centrifuging, drying and grinding the mixed liquid B to obtain the biomass magnetic adsorbent.
3. The method for preparing a magnetic adsorbent by using the waste zinc-manganese battery and the biomass as claimed in claim 2, wherein in the step 1, the particle size of the electrode powder is less than 125 μm.
4. The method for preparing the magnetic adsorbent by using the waste zinc-manganese battery and the biomass as claimed in claim 2, wherein the solvent of the nutrient salt is water, and the solutes of the nutrient salt are as follows: (NH) in an amount of 1.0 to 3.0g/L 4 ) 2 SO 4 KH with the content of 1.0-2.0 g/L 2 PO 4 MgSO 1.0-2.0 g/L MgSO 4 ·7H 2 O and CaCl with the content of 0.25-0.5 g/L 2 ；
The solvent of the mixed energy substrate is water, the content of the sulfur powder is 5-15 g/L, and the content of the ferrous sulfate is 10-30 g/L.
5. The method for preparing the magnetic adsorbent by using the waste zinc-manganese battery and the biomass as claimed in claim 2, wherein in the inoculation and cultivation process of the step 2: the rotating speed of the shaking table is 120 r/min-160 r/min, the temperature is 30-40 ℃, and the cultivation days are 3-5 days.
6. The method for preparing the magnetic adsorbent by using the waste zinc-manganese battery and the biomass as claimed in claim 2, wherein in the leaching process of the step 3, the rotating speed of the shaking table is 120 r/min-160 r/min, and the leaching time is 1 h-2 h.
7. The method for preparing magnetic adsorbent by using waste zinc-manganese battery and biomass as claimed in claim 2,in the step 3: the Mn is 1-x Zn x Fe 2 O 4 In the magnetic material preparation liquid, the total concentration of Zn ions, mn ions and Fe ions is 12 mol/L-2 mol/L, and x is 0.2-0.6.
8. The method for preparing the magnetic adsorbent by using the waste zinc-manganese battery and the biomass as claimed in claim 2, wherein in the step 4: the biomass is one of sawdust, peanut shell powder, corn straw, dried leaves, peach kernel powder and apricot kernel powder.
9. The method for preparing the magnetic adsorbent by using the waste zinc-manganese battery and the biomass as claimed in claim 2, wherein the mass ratio of the electrode powder to the biomass is 1:1-3.
10. The method for preparing the magnetic adsorbent by using the waste zinc-manganese battery and the biomass as claimed in claim 2, wherein in the step 4: the mass fraction of the NaOH solution is 10-30%, and the stirring time is 1.0-3.0 h; the reaction temperature in the high-pressure reaction tank is 180-220 ℃, and the reaction time is 5-12 h.
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Application publication date: 20171107 Assignee: Yan'an Yiqiang industry and Trade Co.,Ltd. Assignor: YAN'AN University Contract record no.: X2022980003366 Denomination of invention: A method for preparing magnetic adsorbent from waste zinc manganese battery and biomass Granted publication date: 20200811 License type: Exclusive License Record date: 20220328 |