CN111389363B - Magnetic biochar adsorbing material based on sulfate-reduced sludge and preparation method and application thereof - Google Patents

Magnetic biochar adsorbing material based on sulfate-reduced sludge and preparation method and application thereof Download PDF

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CN111389363B
CN111389363B CN202010253815.6A CN202010253815A CN111389363B CN 111389363 B CN111389363 B CN 111389363B CN 202010253815 A CN202010253815 A CN 202010253815A CN 111389363 B CN111389363 B CN 111389363B
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sludge
iron
sulfate
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CN111389363A (en
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钱进
许向宁
马蕊
张明宽
闫雪倩
王玉珏
徐欢
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405 Geological Team Of Sichuan Geological And Mineral Exploration And Development Bureau
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

The invention relates to the technical field of biomass resource utilization, and provides a magnetic biochar adsorbing material based on sulfate-reduced sludge, and a preparation method and application thereof. According to the invention, sulfate-reduced sludge is used as a raw material, dried sulfate-reduced sludge is compounded with an iron-containing solution to obtain iron-containing sludge, and then the iron-containing sludge is subjected to pyrolysis to obtain the magnetic biochar adsorbing material. According to the invention, the magnetic biochar adsorbing material is prepared by using sulfate reduced sludge, the adsorption performance of the carbon material is improved by adding iron ions, the preparation steps are simple, the cost is low, the production efficiency is high, modifiers such as N source and S source are not required to be additionally added, the large-scale production is facilitated, the resource recycling of the sulfate reduced residual sludge can be realized, the obtained magnetic biochar adsorbing material has a good adsorption effect on heavy metals and dyes, and the magnetic separation performance is good.

Description

Magnetic biochar adsorbing material based on sulfate-reduced sludge and preparation method and application thereof
Technical Field
The invention relates to the technical field of biomass resource utilization, in particular to a magnetic biochar adsorbing material based on sulfate-reduced sludge, and a preparation method and application thereof.
Background
With the rapid development of the industry, the economy is rapidly increased, and meanwhile, the serious environmental pollution problem is caused. In waste liquid generated in industrial production processes of papermaking, leather making, petrochemical industry, pharmacy, molasses fermentation, acid mine waste water, flue gas desulfurization and denitration and the like, the concentration of sulfate is extremely high. The sludge biological treatment technology provides an important means for the treatment of the current high-concentration organic wastewater, can realize the purposes of greatly reducing organic pollutants and effectively recovering energy with lower treatment cost, and is widely applied to water treatment processes all over the world.
Originated by Chenglihao team of hong Kong science and technology university
Figure BDA0002436476340000011
The technology is a new technology for treating high-salt urban sewage based on the integration of heterotrophic Sulfate reduction (Sulfate reduction), Autotrophic denitrification (Autotrophic denitrification) and nitrification reaction (nitrification), wherein sulfur plays a role of circulating electron carriers, organic pollutants are oxidized and alkalinity is generated through sulfur circulation, and a large amount of electrons flow to SO through a heterotrophic metabolic pathway4 2-And generates solubility S2-S flowing into anoxic reactor2-Providing electrons for autotrophic denitrification, and generating NO by the nitrification process3 -Conversion to N2The biological denitrification is realized, and the carbon and nitrogen are circularly connected by introducing the sulfur cycle, so that pollutants such as carbon, nitrogen, phosphorus and the like are removed, and one third of energy consumption in the sewage treatment process can be effectively saved.
Although the novel biological treatment process has the advantages of stable operation, high treatment load, low treatment cost and the like, excess sludge (namely sulfate-reduced sludge) can still be generated in the sulfate-reduced phase. Conventional sludge treatment techniques include landfill, land use and incineration, but the use of conventional sludge treatment methods may cause secondary environmental pollution due to heavy metals, organic pollutants and pathogens that may be contained in the sludge.
Disclosure of Invention
In view of the above, the invention provides magnetic biochar based on sulfate-reduced sludge, and a preparation method and application thereof. The magnetic biochar adsorbing material with the adsorption effect and the magnetic separation characteristic is prepared by utilizing the sulfate-reduced sludge, so that the sulfate-reduced sludge can be recycled, and the obtained magnetic biochar adsorbing material is good in magnetism and high in adsorption capacity, and can effectively adsorb heavy metals and dyes.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a magnetic biochar adsorbing material based on sulfate-reduced sludge comprises the following steps:
(1) sequentially sieving, cleaning and drying the sulfate-reduced sludge to obtain dried sludge;
(2) mixing the dried sludge and the iron-containing solution, adjusting the pH value of the mixed solution to be alkaline, and then sequentially stirring, centrifuging, cleaning and drying to obtain iron-containing sludge; the iron ions in the iron-containing solution include Fe2+And Fe3+；
(3) And pyrolyzing the iron-containing sludge under a protective atmosphere to obtain the magnetic biochar adsorbing material based on sulfate-reduced sludge.
Preferably, the sieving in the step (1) is to pass through a sieve with 18-30 meshes, and take undersize products; the drying temperature in the step (1) is 70-100 ℃.
Preferably, the iron-containing solution is a mixed solution of ferrous sulfate and ferric chloride; fe in the iron-containing solution2+The concentration of (A) is 2.5-3 g/L; fe in the iron-containing solution2+And Fe3+The molar ratio of (A) to (B) is 1: 1.75-2.
Preferably, the dosage ratio of the dried sludge to the iron-containing solution is 1-4 g: 200 mL.
Preferably, the method for adjusting the pH of the mixed solution to be alkaline comprises: and adjusting the pH value of the mixed solution to 10-12 by using a NaOH solution.
Preferably, the stirring is magnetic stirring, and the stirring time is 30-60 min.
Preferably, the rotating speed of the centrifugation is 2000-4000 rpm, and the time of the centrifugation is 10-20 min.
Preferably, the pyrolysis temperature is 500-600 ℃, the time is 2-3 h, and the heating rate of heating to the pyrolysis temperature is 5-10 ℃/min.
The invention also provides the magnetic biochar adsorbing material prepared by the preparation method in the scheme.
The invention also provides application of the magnetic biochar adsorbing material in the scheme in adsorption of heavy metals and/or dyes.
Has the advantages that:
(1) according to the invention, the sulfate-reduced sludge is used for preparing the magnetic biochar adsorbing material, sulfur enriched in the sulfate-reduced sludge has a modification effect on biochar materials, and sulfur elements are still effectively retained in the prepared magnetic biochar adsorbing material;
(2) in the invention, Fe is added in the process of preparing the magnetic material2+And Fe3+Under alkaline conditions, part of the iron ions form Fe3O4Part of iron ions can be combined with S element in sludge to form FeS, so that the surface roughness of the magnetic biochar adsorbing material particles can be increased, the specific surface area and the pore volume of the obtained magnetic biochar adsorbing material are effectively increased, the pore structure of the magnetic biochar adsorbing material is richer, the surface adsorbing functional groups and the adsorbing sites are increased, and the adsorption and removal capacity of pollutants such as heavy metals, dyes and the like is enhanced;
(3) in the preparation process, no chemical modifiers such as S source, N source and the like are added, the preparation steps are simple, the cost is low, the production efficiency is high, the large-scale production is facilitated, the sulfate-reduced excess sludge can be recycled, and the problems of recycling and treatment of the excess sludge are solved;
(4) the magnetic biochar adsorption material prepared by the invention has the advantages of large specific surface area, high adsorption capacity and good adsorption effect on heavy metals and dyes, and can be separated and recycled by utilizing magnetism after adsorption is finished.
Drawings
FIG. 1 is a schematic diagram of a technical scheme for preparing a magnetic biochar adsorbent based on sulfate-reduced sludge in example 1;
figure 2 is a scanning electron microscope image of SBC-5-500, SBC-10-500, SBC-20-500, and SBC-500;
figure 3 shows SBC-5-500SBC-10-500, SBC-20-500 and N of SBC-5002Adsorption-desorption isotherms;
figure 4 is a graph of the results of a magnetic separation capacity test of SBC-5-500 in soil (a) and solution (b);
figure 5 is an element distribution diagram for SBC-500 and SBC-20-500.
Detailed Description
The invention provides a preparation method of a magnetic biochar adsorbing material based on sulfate-reduced sludge, which comprises the following steps:
(1) sequentially sieving, cleaning and drying the sulfate-reduced sludge to obtain dried sludge;
(2) mixing the dried sludge and the iron-containing solution, adjusting the pH value of the mixed solution to be alkaline, and then sequentially stirring, centrifuging, cleaning and drying to obtain iron-containing sludge; the iron ions in the iron-containing solution include Fe2+And Fe3+；
(3) And pyrolyzing the iron-containing sludge under a protective atmosphere to obtain the magnetic biochar adsorbing material based on sulfate-reduced sludge.
According to the invention, sulfate-reduced sludge is sequentially screened, cleaned and dried to obtain dried sludge. In the invention, the sulfate-reduced sludge is excess sludge generated in a sulfate-reduced phase in the process of treating sulfate-containing sewage, and the excess sludge contains a large amount of synthesized cytoskeletal proteins and DNA structural elements such as silicon and oxides thereof, sulfur and oxides thereof, C, N, P and the like, and microbial synthesized self-cell trace elements such as zinc, manganese, calcium, nickel, magnesium and the like. The present invention has no particular requirement on the source of the sulfate-reduced sludge, and sulfate-reduced sludge known to those skilled in the art may be used. In a specific embodiment of the present invention, the sulfate-reduced sludge is preferably obtained by laboratory culture by the following method: using a UASB reactor, setting Hydraulic Retention Time (HRT) to be 4-8 h, preferably 6h when the reactor runs stably, adding an organic carbon source into the reactor, and controlling SO in inlet water based on S element4 2-The concentration is 200-300 mg.L-1Preferably 250 mg.L-1In the water S2-The concentration is 120-200 mg L-1Preferably 130 to 150 mg.L-1And stably running for 50-80 days, preferably 65 days, wherein the residual sludge at the bottom of the reactor is the sulfate-reduced sludge. In the present invention, the organic carbon source is preferably glucose and yeast; the feed water is preferably formulated using sodium sulfate as the sulfur source.
In the invention, the sulfate-reduced sludge is sieved preferably by 18-30 meshes, more preferably by 20-24 meshes, and undersize products are taken.
In the present invention, the washing is preferably performed 3 times using deionized water.
In the invention, the drying is preferably drying, and the drying temperature is preferably 70-100 ℃, more preferably 80-90 ℃; the method has no special requirement on the drying time, and can completely remove the water in the washed sulfate-reduced sludge. According to the invention, the dried sludge is preferably ground and then sieved by a 100-mesh sieve, and the obtained dried sludge powder is subjected to subsequent treatment.
After the dried sludge is obtained, the dried sludge and the iron-containing solution are mixed, the pH value of the mixed solution is adjusted to be alkaline, and then stirring, centrifuging, cleaning and drying are sequentially carried out to obtain the iron-containing sludge. In the present invention, the iron ions in the iron-containing solution include Fe2+And Fe3+(ii) a The iron-containing solution is preferably a mixed solution of ferrous sulfate and ferric chloride; fe in the iron-containing solution2+The concentration of (b) is preferably 2.5-3 g/L, and more preferably 2.688 g/L; fe in the iron-containing solution2+And Fe3+The molar ratio of (a) to (b) is preferably 1:1.75 to 2, more preferably 1: 1.8 to 1.9.
In the invention, the preferable dosage ratio of the dried sludge to the iron-containing solution is 1-4 g: 0.2L, specifically 1 g: 0.2L, 2 g: 0.2L, 3 g: 0.2L or 4 g: 0.2L.
In the present invention, the method of adjusting the pH of the mixed solution to alkalinity is: adjusting the pH value of the mixed solution to 10-12, preferably 10.5-11.0 by using NaOH solution; the concentration of the NaOH solution is preferably 10 mol/L.
In the present inventionThe stirring is preferably magnetic stirring, and the stirring time is preferably 30-60 min, and more preferably 40-50 min; the invention preferably uses tin foil to seal the mouth of the container during the magnetic stirring process. The iron ions in the iron solution form Fe under alkaline conditions3O4(the specific reaction process is shown as formula 1), drying the sludge and Fe3O4Fully contact and mix under the stirring action, and finally coat the sludge on Fe3O4On the surface, in addition, part of the iron ions are combined with S in the sludge to form FeS.
2Fe3++Fe2++8OH-1→2Fe(OH)3Fe(OH)2(s)→Fe3O4(s)+4H2O is represented by the formula 1.
In the invention, the rotation speed of the centrifugation is preferably 2000-4000 rpm, more preferably 2500-3500 rpm, the time of the centrifugation is preferably 10-20 min, more preferably 15min, after the centrifugation is finished, the supernatant is poured off, and the bottom sediment is cleaned.
In the present invention, the washing is preferably centrifugal washing, specifically: adding ultrapure water into the precipitate obtained by centrifugation, centrifuging at 2000-4000 rpm for 10-20 min, pouring the supernatant, and repeating the above processes until the supernatant is colorless.
After the cleaning is finished, the cleaning product is dried to obtain the iron-containing sludge. In the present invention, the temperature of the drying is preferably 80 ℃; the method has no special requirement on the drying time, and can completely remove the water in the washed sulfate-reduced sludge.
After the iron-containing sludge is obtained, the iron-containing sludge is pyrolyzed under a protective atmosphere to obtain the magnetic biochar adsorbing material based on sulfate-reduced sludge. In the invention, the protective atmosphere is preferably nitrogen, the pyrolysis temperature is preferably 500-600 ℃, more preferably 530-580 ℃, the time is preferably 2-3 h, more preferably 2.0-2.5 h, and the heating rate of heating to the pyrolysis temperature is preferably 5-10 ℃/min, more preferably 8-10 ℃/min; the pyrolysis is preferably carried out in a tube furnace, and in particular embodiments of the invention, the dried sludge is preferably placed in tin foilThe paper is then laid in a quartz boat and placed in a tube furnace for pyrolysis. Along with the progress of the pyrolysis process, the content of C and ash in the biochar is gradually increased, N, H, the content is reduced, and Fe3O4After pyrolysis, the product is Fe2O3And Fe3O4A mixture of (a).
After pyrolysis is finished, the obtained pyrolysis product is preferably ground and sieved to obtain the magnetic biochar adsorbing material; the screening is preferably carried out by screening with a 80-120-mesh sieve, and undersize products are taken.
The invention also provides the magnetic biochar adsorbing material prepared by the preparation method in the scheme. The magnetic biochar adsorbing material provided by the invention has the advantages of large specific surface area, large pore volume, rich pore structure, many surface adsorption functional groups and adsorption sites, strong adsorption and removal capacity for pollutants such as heavy metals, dyes and the like, and good magnetic separation capacity. In the invention, the BET specific surface area of the magnetic biochar adsorbing material is preferably 33.2285-41.1929 m2The specific surface area of Langmuir is preferably 51.26-63.87 m2The total pore volume is preferably 0.0905-0.1198 mL/g, and the average pore diameter is preferably 8.7879-14.1481 mL/g.
The invention provides application of the magnetic biochar adsorbing material in the scheme in adsorption of heavy metals and/or dyes. In a specific embodiment of the present invention, the magnetic biochar adsorbent is preferably used for removing heavy metals and/or dyes from sewage or soil, and after adsorption is completed, the magnetic biochar adsorbent can be separated by using a magnet. The present invention does not require any particular method for the specific operation of the adsorption, and methods known to those skilled in the art can be used.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
The sulfate-reduced sludge used in the examples was sulfate-reduced sludge cultured in a long period in a laboratory, a UASB reactor was used as an experimental apparatus, HRT was 6 hours, glucose and yeast were used as organic carbon sources, and Na was used as Na2SO4As sulfur source, calculated as S element, feed water SO4 2-The concentration is 250 mg.L-1And water is discharged S2-The concentration is stabilized at 120 +/-10 mg.L-1And stable operation 65 d.
Example 1
Taking 2L of sulfate-reduced sludge cultured in a laboratory for a long time, sieving (20 meshes, 0.841mm), washing with deionized water for 3 times, drying the sludge in an oven at 80 ℃, grinding into powder by a mortar, sieving by a 100-mesh (0.154mm) sieve, storing the obtained dried sludge powder in a sample bag, sealing, drying and storing.
Preparation of a composition containing ferrous sulfate (FeSO)4·7H2O) and iron chloride (FeCl)3·6H2O) 1L iron solution (Fe in it)2+Has a content of 2.688g/L, Fe3+Has a content of 4.704g/L, Fe2+And Fe3+The molar ratio of the dried sludge to the dried sludge is 1:1.75), 2g of dried sludge and 400mL of iron solution are uniformly mixed in a 500mL glass beaker, the mixture is placed on a magnetic stirrer, the pH value of the mixture is adjusted to 10 by using 10mol/L NaOH solution, the mixture is sealed by using tin foil paper, and the mixture is stirred for 30min, so that the solution and the dried sludge powder are uniformly mixed for later use.
Centrifuging the obtained mixed solution at 3000rpm for 10min, pouring out the supernatant, adding 100mL of deionized water into a centrifuge bottle, shaking up, further cleaning, centrifuging at 3000rpm for 10min, pouring out the supernatant, repeating the above processes until the supernatant is colorless, and drying the obtained product in an oven at 80 ℃ to obtain the iron-containing sludge.
Putting the obtained iron-containing sludge into a quartz boat, putting the quartz boat into a tubular furnace, and adding N2Heating to 500 ℃ at a heating rate of 10 ℃/min under a protective atmosphere for pyrolysis, keeping for 2h, cooling to room temperature, taking out, grinding and sieving (100 meshes, 0.154mm), storing the obtained material in a sample bag, sealing, drying and storing, thus finishing the preparation of the magnetic biological adsorption material, and naming the prepared magnetic biological carbon adsorption material as SBC-5-500 according to the ratio of the mass (g) of the dried sludge to the volume (L) of the iron solution, wherein the specific preparation flow of example 1 is shown in figure 1.
Example 2
The preparation steps are the same as example 1, except that 4g of dried sludge and 400mL of iron solution are uniformly mixed in a 500mL glass beaker, the other preparation processes are the same, and the prepared magnetic biochar adsorbing material is named as SBC-10-500 according to the ratio of the mass (g) of the dried sludge to the volume (L) of the iron solution.
Example 3
The preparation steps are the same as example 1, except that 8g of dried sludge and 400mL of iron solution are uniformly mixed in a 500mL glass beaker, the other preparation processes are the same, and the prepared magnetic biochar adsorbing material is named as SBC-20-500 according to the ratio of the mass (g) of the dried sludge to the volume (L) of the iron solution.
Comparative example 1
The other steps are the same as the example 1, except that the dried sludge powder is directly pyrolyzed without adding the iron-containing solution, and the obtained prepared biochar material is named as SBC-500.
And (3) characterization results:
(1) appearance characterization
Scanning electron microscope observation was performed on SBC-5-500, SBC-10-500, SBC-20-500 and SBC-500 prepared in examples 1 to 3 and comparative example 1, and the results are shown in FIG. 2; as can be seen from FIG. 2, SBC-5-500, SBC-10-500 and SBC-20-500 exhibit a rough and uneven morphology of the magnetic biochar surface with irregular nanoparticles after magnetic modification, as compared to SBC-500.
(2) Analysis of physicochemical Properties
The SBC-5-500, SBC-10-500, SBC-20-500, and SBC-500 prepared in examples 1 to 3 and comparative example 1 were characterized for pH, ash, BET specific surface area, Langmuir specific surface area, total pore volume, and average pore diameter, and the yield of the carbon material (yield: mass of magnetic biochar material after pyrolysis/mass of material before pyrolysis) was calculated, and the results obtained are shown in table 1.
TABLE 1 results of analysis of physicochemical Properties of SBC-5-500, SBC-10-500, SBC-20-500, and SBC-500
Figure BDA0002436476340000081
As can be seen from Table 1, the BET specific surface area of SBC-5-500 is significantly improved and the total pore volume is improved by nearly 3 times, compared with the biochar material (SBC-500) which is not magnetically modified by adding Fe, the specific surface area and the pore volume of SBC-10-500 and SBC-2-500 are also greatly improved compared with SBC-500, the pH value of SBC-5-500, SBC-10-500 and SBC-20-500 is increased compared with SBC-500, and the yield is also greatly improved, wherein the yield of SBC-5-500 reaches 84.32%.
(3) Adsorption-desorption isotherm
Figure 3 is a drawing of N for SBC-5-500, SBC-10-500, SBC-20-500, and SBC-5002Adsorption-desorption isotherms; as can be seen from fig. 3, the adsorption curve of SBC-5-500 prepared in example 1 is concentrated in the middle-high pressure section, and conforms to the type IV isotherm, which indicates that the biochar material is mainly of a mesoporous structure, and the adsorption capacity is significantly improved compared with other examples; and from figure 3, it can be seen that SBC-5-500, SBC-10-500 and SBC-20-500 all have higher adsorption capacities than SBC-500.
(4) Magnetic separation Capacity test
Testing the magnetic separation capability of the SBC-5-500, namely testing the magnetic biochar adsorbing material of the SBC-5-500 respectively dispersed in a water body solution and soil by adopting a strong magnet, wherein the magnetic separation capability test result is shown in figure 4, wherein (a) is the magnetic separation capability test result of the SBC-5-500 in the soil, and (b) is the magnetic separation capability test result of the SBC-5-500 in the solution; as can be seen from FIG. 4, soil was mixed with a magnetic biochar adsorbent, a strong magnet was placed over the sample tube, and the magnetic biochar adsorbent was adsorbed on the top of the tube; in aqueous solution, the magnetic biochar adsorbing material can be adsorbed on the side wall of the sample tube by strong magnets without falling off, which shows that the magnetic biochar adsorbing material prepared by the invention has excellent magnetic separation capability in a solid-solid phase and a solid-liquid phase.
The same magnetic separation capability test was performed for SBC-10-500 and SBC-20-500, and the results were similar to those for SBC-5-500.
(5) Elemental distribution analysis
EDS analysis is performed on SBC-500 and SBC-20-500, the obtained element distribution map is shown in figure 5, the left side of figure 5 is the element distribution map of SBC-500, and the right side is the element distribution map of SBC-20-500, and it can be seen from figure 5 that C, O, S elements are effectively reserved and distributed uniformly in the process of preparing the biochar by pyrolyzing sludge. Through magnetic modification, the SBC-20-500 is successfully doped with Fe element and is uniformly distributed.
EDS analysis is carried out on SBC-5-500 and SBC-10-500, and results show that Fe elements are uniformly distributed.
Example 4
The magnetic biochar adsorbent SBC-5-500 contains 35 mg.L-1The application of Cr (VI) polluted wastewater specifically comprises the following steps:
0.2g of SBC-5-500 prepared in example 1 was weighed, and 30mL of 35 mg. L-1Cr (VI) solution is added into a screw cap sample bottle respectively and then 0.6MHNO is used3And 0.1M NaOH solution, adjusting pH to 3, covering and sealing, placing into a constant temperature shaking table, controlling the temperature to be 25 ℃, controlling the rotating speed to be 200rpm, after reacting for 13h, the adsorption capacity of SBC-5-500 to Cr (VI) is 5.21mg/g, the removal rate of Cr (VI) reaches 99%, and after reacting for 13h, the concentration of Cr (VI) in the solution is 0.27mg/L, and the discharge requirement that the concentration of Cr (VI) in the wastewater discharge standard (GB8978-1996) in China is lower than 0.5mg/L is met; after 24 hours of reaction, no Cr (VI) can be detected in effluent, and the adsorption capacity of SBC-5-500 for Cr (VI) is 5.25 mg/g. During the adsorption process, the pH value of the solution has a rising trend, the pH value is adjusted to be 3 at the initial time, and the pH value of the solution is 6.76 after 48 hours, so the material has better improvement effect on the adjustment and treatment of the acidic wastewater.
Example 5
The magnetic biochar adsorbent SBC-5-500 contains 120 mg.L-1The application of Cr (VI) polluted wastewater specifically comprises the following steps:
0.2g of SBC-5-500 prepared in example 1 was weighed out, and 30mL of 120 mg. multidot.L was taken-1Cr (VI) solution is added into a screw cap sample bottle respectively and then 0.6MHNO is used3And 0.1M NaOH solution, adjusting the pH value to 3, covering and sealing, putting into a constant temperature shaking table, controlling the temperature to be 25 ℃, rotating speed to be 200rpm, controlling the adsorption capacity of SBC-5-500 to Cr (VI) to be 11.60mg/g after reacting for 13h, controlling the adsorption capacity to Cr (VI) to be 13.17mg/g after reacting for 24h, and controlling the adsorption capacity to Cr (VI) to be 18 after reacting for 48 h.64mg/g, and during the adsorption process, the pH of the solution had a tendency to rise, with an initial pH adjustment of 3 and a solution pH of 6.75 after 48 h.
Example 6
The magnetic biochar adsorbent SBC-5-500 contains 100 mg.L-1The application of the methyl orange dye in the wastewater specifically comprises the following steps:
0.2g of SBC-5-500 of example 1 was weighed, and 50mL of methyl orange was weighed to a concentration of 100 mg. L-1The solutions of (4) were added separately to screw-cap sample bottles using 0.6MHNO3And 0.1M NaOH solution, adjusting the pH value to 7 +/-0.1, covering and sealing, putting into a constant-temperature shaking table, controlling the temperature to be 25 ℃ and the rotating speed to be 200rpm, and after reacting for 2 hours, enabling the adsorption removal rate of SBC-5-500 on methyl orange to reach 100%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a magnetic biochar adsorbing material based on sulfate-reduced sludge is characterized by comprising the following steps:
(1) sequentially sieving, cleaning and drying the sulfate-reduced sludge to obtain dried sludge;
(2) mixing the dried sludge and the iron-containing solution, adjusting the pH value of the mixed solution to be alkaline, and then sequentially stirring, centrifuging, cleaning and drying to obtain iron-containing sludge; the iron ions in the iron-containing solution include Fe2+And Fe3+(ii) a Fe in the iron-containing solution2+And Fe3+The molar ratio of (A) to (B) is 1: 1.75-2;
(3) and pyrolyzing the iron-containing sludge under a protective atmosphere to obtain the magnetic biochar adsorbing material based on sulfate-reduced sludge.
2. The preparation method according to claim 1, wherein the sieving in the step (1) is 18-30 mesh sieving, and undersize products are taken; the drying temperature in the step (1) is 70-100 ℃.
3. The production method according to claim 1, wherein the iron-containing solution is a mixed solution of ferrous sulfate and ferric chloride; fe in the iron-containing solution2+The concentration of (b) is 2.5-3.0 g/L.
4. The preparation method according to claim 1 or 3, wherein the dosage ratio of the dried sludge to the iron-containing solution is 1-4 g: 0.2L.
5. The method of claim 1, wherein the method of adjusting the pH of the mixed solution to alkaline comprises: and adjusting the pH value of the mixed solution to 10-12 by using a NaOH solution.
6. The preparation method according to claim 1, wherein the stirring is magnetic stirring, and the stirring time is 30-60 min.
7. The preparation method according to claim 1, wherein the rotation speed of the centrifugation is 2000-4000 rpm, and the time of the centrifugation is 10-20 min.
8. The preparation method according to claim 1, wherein the pyrolysis temperature is 500-600 ℃, the time is 2-3 h, and the heating rate for heating to the pyrolysis temperature is 5-10 ℃/min.
9. The magnetic biochar adsorbing material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the magnetic biochar adsorbent material according to claim 9 for adsorbing heavy metals and/or dyes.
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