CN113042519B - Biological type zero-valent iron sulfide material and preparation method and application thereof - Google Patents

Biological type zero-valent iron sulfide material and preparation method and application thereof Download PDF

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CN113042519B
CN113042519B CN202110306684.8A CN202110306684A CN113042519B CN 113042519 B CN113042519 B CN 113042519B CN 202110306684 A CN202110306684 A CN 202110306684A CN 113042519 B CN113042519 B CN 113042519B
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valent iron
zero
iron sulfide
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sulfide material
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CN113042519A (en
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李骞
许瑞
陈许玲
南小龙
姜涛
杨永斌
金胜明
尹华群
蒋国清
姜必广
徐斌
王丽敏
尹哲
董斯宇
韩雨琪
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No36 Brigade Of Hunan Nuclear Industry Geological Bureau
Central South University
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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    • B09C2101/00—In situ
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

A biological type zero-valent iron sulfide material, a preparation method and application thereof, belonging to the technical field of heavy metal pollution remediation. The invention utilizes the template material, combines a biological reduction method and a chemical reduction method, and synthesizes the zero-valent iron sulfide material under the combined action of sulfate reducing bacteria and a reducing agent. In addition, in the synthesis process, sulfate reducing bacteria and metabolites thereof are loaded on the surface and in pores of the template material, so that various active groups are added to the material, and the adsorption effect of the material on metal ions is enhanced. Compared with the material synthesized by a direct chemical method, the sulfuration zero-valent iron material prepared by the method has better electron transfer performance, adsorption performance and dispersion performance. The raw materials adopted by the invention are all environment-friendly, the preparation process of the materials is simple, the cost is low, the adsorption efficiency is high, and the heavy metals in soil and water can be simultaneously repaired.

Description

Biological type zero-valent iron sulfide material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of heavy metal pollution remediation, and particularly relates to a biological type zero-valent iron sulfide material, a preparation method thereof and application thereof in heavy metal polluted soil and water.
Background
With the acceleration of the industrialization and urbanization processes, the pollution of heavy metals such As chromium (Cr), arsenic (As), cadmium (Cd), copper (Cu), mercury (Hg), lead (Pb), selenium (Se), zinc (Zn), nickel (Ni) and the like in soil is increasingly serious. Heavy metals are a major threat to human and environmental health due to their non-biodegradability, high toxicity, persistence, and possible constant accumulation in the organism through the food chain. Heavy metals interact strongly with proteins and various enzymes in the human body, deactivating them, resulting in various diseases in humans, including cardiovascular diseases, cancer, chronic anemia, and damage to the kidneys, nervous system, brain, skin and bones. For example, cadmium can cause hypertension, cause cardiovascular and cerebrovascular disease, damage bone and liver and kidney, and cause renal failure; lead is a highly toxic substance to heavy metal contamination and is difficult to remove once it enters the human body. Can directly damage brain cells of human, especially nervous system of fetus, and can cause congenital mental retardation. Therefore, the method has important significance for repairing the heavy metal contaminated soil and recovering the soil function and improving the agricultural sustainable development and the environmental quality.
The restoration of heavy metal polluted sites is generally divided into a chemical method, a physical method and a biological method, and the restoration technology mainly comprises natural purification, soil cleaning, soil dressing, thermal desorption, vitrification, electric extraction, solidification/stabilization, biological restoration and the like. In recent years, iron-based materials (such as goethite, hematite, amorphous fe (feooh), magnetite, zero-valent iron) have been widely used for remediation of heavy metal pollution in soil due to their characteristics of easy production, low cost, eco-friendliness, and low maintenance. Among them, zero-valent iron (ZVI) has advantages of large specific surface area, high reactivity, few intermediates, environmental friendliness, and the like, and thus has received much attention. However, ZVI tends to agglomerate and passivate, resulting in reduced mobility and reactivity, thereby limiting the scale-up of zero-valent iron technology.
Disclosure of Invention
In view of the above, the present invention aims to provide a biological zero-valent iron sulfide material, a preparation method thereof, and applications thereof in heavy metal contaminated soil and water. The invention uses the template material to prepare the zero-valent iron sulfide material, so that ZVI is not easy to agglomerate and passivate, the dispersibility is good, and the adsorption effect on heavy metal ions is enhanced.
The invention provides a preparation method of a biological type zero-valent iron sulfide material, which comprises the following steps:
adding the template material into a sulfate reducing bacteria culture medium, and carrying out anaerobic sterilization to obtain a sterilized culture solution;
mixing the sterilized culture solution with ferrous salt, inoculating sulfate reducing bacteria, and carrying out microbial reduction in an anaerobic environment to obtain a microbial reduced matter;
and mixing the microbial reductant and a reducing agent in an inert gas atmosphere to carry out chemical reduction reaction to obtain the biological zero-valent iron sulfide material.
Preferably, the sulfate-reducing bacteria culture medium comprises the following components in concentrations: KH (Perkin Elmer)2PO40.5±0.05g/L，NH4Cl 1±0.05g/L，CaSO4·2H2O 1±0.05g/L，MgSO42 plus or minus 0.1g/L, 5 plus or minus 0.1g/L sodium citrate, 3.5 plus or minus 0.1g/L sodium lactate and 1 plus or minus 0.05g/L yeast extract.
Preferably, the template material comprises one or more of kaolin, talcum powder and white carbon black.
Preferably, the liquid-solid ratio of the template material added in the sulfate reducing bacteria culture medium is 100: 0.5-3.
Preferably, the ferrous salt is FeSO4·7H2O and/or Fe (NH)4)2·(SO4)2·6H2O。
Preferably, the mixed solution obtained after mixing the sterilization culture solution and ferrous salt is Fe2+The concentration of (b) is 0.14-0.5 g/L.
Preferably, the inoculation amount of the sulfate-reducing bacteria in the sterilized culture solution is not less than 1.0X 107CFU/mL。
Preferably, the reducing agent is borohydride.
The invention also provides the biological type zero-valent iron sulfide material prepared by the preparation method in the technical scheme, wherein the aperture of the biological type zero-valent iron sulfide material is 20-60 nm, and the specific surface area is 150-400 m2The porosity is 40-60 percent.
The invention also provides application of the biological zero-valent iron sulfide material in the technical scheme in repairing heavy metal contaminated soil and water.
The invention provides a preparation method of a biological type zero-valent iron sulfide material, which comprises the following steps: adding the template material into a sulfate reducing bacteria culture medium, and carrying out anaerobic sterilization to obtain a sterilized culture solution; mixing the sterilized culture solution with ferrous salt, inoculating sulfate reducing bacteria, and carrying out microbial reduction in an anaerobic environment to obtain a microbial reduced matter; and mixing the microbial reductant and a reducing agent in an inert gas atmosphere to carry out chemical reduction reaction to obtain the biological zero-valent iron sulfide material.
According to the invention, the template material is adopted, the microbial reduction method and the chemical reduction method are combined, the zero-valent iron sulfide material is synthesized under the combined action of the sulfate reducing bacteria and the reducing agent, the template material has large specific surface area and good dispersibility and chemical stability, iron and sulfur elements formed by biological reduction, the sulfate reducing bacteria and metabolites thereof are uniformly dispersed on the template material through microbial mediation, and the occurrence of agglomeration phenomenon can be effectively prevented, so that the adsorption efficiency is improved, and the effect of permanently repairing heavy metal pollution is achieved; in the preparation process, sulfate reducing bacteria and metabolites thereof are loaded on the surface and in pores of the template material, and extracellular substances such as amino acid, nucleotide, polysaccharide, lipid and the like can be generated in the propagation process of the sulfate reducing bacteria, so that various active groups are added to the material, the effects of complexing and precipitating heavy metal ions are achieved, and the adsorption effect of the material on the heavy metal ions is enhanced. The zero-valent iron sulfide material prepared by the method has strong dispersibility and high interfacial activity, and can be used for repairing soil and water bodies singly or compositely polluted by Pb, Cu, Zn and Cd.
Furthermore, the template material comprises one or more of kaolin, talcum powder and white carbon black, the kaolin, the talcum powder and the white carbon black are all natural minerals which are cheap and easy to obtain, raw materials are easy to obtain, and the production cost is low.
The biological iron sulfide material provided by the invention has the aperture of 20-60 nm and the specific surface area of 150-400 m2The porosity is 40% -60%, the material has the repairing performance of sulfate reducing bacteria and a zero-valent iron sulfide material, and heavy metals are removed through adsorption, reduction, complexation and sulfide precipitation. The material provided by the invention is not only suitable for soil remediation singly or compositely polluted by heavy metals Pb, Cu, Zn and Cd, but also suitable for wastewater purification singly or compositely polluted by heavy metals Pb, Cu, Zn and Cd.
Drawings
FIG. 1 is a schematic process flow diagram of the preparation of a biological zero-valent iron sulfide material according to example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) spectrum of the biotype zero-valent iron sulfide material prepared in example 1;
Detailed Description
The invention provides a preparation method of a biological type zero-valent iron sulfide material, which comprises the following steps:
adding the template material into a sulfate reducing bacteria culture medium, and carrying out anaerobic sterilization to obtain a sterilized culture solution;
mixing the sterilized culture solution with ferrous salt, inoculating sulfate reducing bacteria, and carrying out microbial reduction in an anaerobic environment to obtain a microbial reduced matter;
and mixing the microbial reductant and a reducing agent in an inert gas atmosphere to carry out chemical reduction reaction to obtain the biological zero-valent iron sulfide material.
The template material is added into a sulfate reducing bacteria culture medium for anaerobic sterilization to obtain a sterilized culture solution.
In the invention, the template material preferably comprises one or more of kaolin, talcum powder and white carbon black, and when the template material is preferably a mixture, the dosage ratio of each substance in the mixture is not particularly limited, and the mixture with any mass ratio can be adopted.
In the invention, the particle size of the template material is preferably 20-60 nm, more preferably 20-30 nm, and most preferably 20 nm; the specific surface area of the template material is preferably 150-400 m2(ii)/g, more preferably 300 to 400m2G, most preferably 400m2The smaller the particle size of the template material is, the larger the specific surface area is, and the better the adsorption effect is.
In the invention, the liquid-solid ratio of the template material added in the sulfate reducing bacteria culture medium is preferably 100: 0.5-3, and most preferably 100: 1.
In the present invention, the sulfate-reducing bacteria medium (modified Baar's medium) preferably includes the following components at the following concentrations: KH (Perkin Elmer)2PO40.5±0.05g/L，NH4Cl 1±0.05g/L，CaSO4·2H2O 1±0.05g/L，MgSO42 plus or minus 0.1g/L, 5 plus or minus 0.1g/L sodium citrate, 3.5 plus or minus 0.1g/L sodium lactate and 1 plus or minus 0.05g/L yeast extract.
In the invention, the sulfate reducing bacteria culture medium is preferably used after the pH value is adjusted, the pH value is preferably 5-8, more preferably 7-8, and most preferably 7.5, and the method for adjusting the pH value is not particularly limited, and can be adjusted by a method known to those skilled in the art.
In the invention, the anaerobic sterilization temperature is preferably 121 ℃, and the time is preferably 15-20 minutes. In the present invention, the anaerobic sterilization is preferably performed in an anaerobic bottle.
After the sterilized culture solution is obtained, the sterilized culture solution and ferrous salt are mixed, then sulfate reducing bacteria are inoculated, and microbial reduction is carried out in an anaerobic environment to obtain a microbial reduction product.
After the anaerobic sterilization is finished, the invention preferably adds ferrous salt after cooling the anaerobic bottle. In the present invention, the ferrous salt is preferably subjected to a filtration sterilization treatment, and the specific operation of the filtration sterilization in the present invention is not particularly limited, and may be performed in a manner known to those skilled in the art.
In the present invention, the ferrous salt is preferably FeSO4·7H2O and/or Fe (NH)4)2·(SO4)2·6H2O, when the ferrous salt is preferably FeSO4·7H2O and Fe (NH)4)2·(SO4)2·6H2In the case of mixtures of O, the invention is directed to FeSO4·7H2O and Fe (NH)4)2·(SO4)2·6H2The mass ratio of O is not particularly limited, and a mixture of any ratio may be used.
In the invention, the time for microbial reduction is preferably 48-72 h, more preferably 60-72 h, most preferably 72h, and the temperature is preferably 28-32 ℃.
In the present invention, the inoculation amount of the sulfate-reducing bacteria in the sterilized culture solution is preferably not less than 1X 107CFU/mL, more preferably 5X 107CFU/mL～10×107CFU/mL. The source of the sulfate-reducing bacteria is not particularly limited in the present invention, and sulfate-reducing bacteria known in the art may be used.
In the present inventionThe mixed solution obtained by mixing the sterilization culture solution and ferrous salt contains Fe2+The concentration of (b) is preferably 0.14 to 0.5g/L, more preferably 0.3g/L, and Fe in the present invention2+The concentration of (A) cannot be too high or too low, when the concentration is too high, the activity of sulfate reducing bacteria is influenced, and when the concentration is too low, the content of iron in the material is lower, and the adsorption capacity is reduced.
The invention preferably inoculates sulfate reducing bacteria in an anaerobic incubator, the microbial reduction preferably being carried out in an anaerobic bottle sealed to ensure an anaerobic environment inside, the microbial reduction preferably being cultured in a thermostatted shaker.
After the microbial reducing substance is obtained, the microbial reducing substance and a reducing agent are mixed for chemical reduction reaction in an inert gas atmosphere to obtain the biological zero-valent iron sulfide material.
In the present invention, the reducing agent is preferably a borohydride, the borohydride is preferably sodium borohydride and/or potassium borohydride, and when the borohydride is preferably a mixture of sodium borohydride and potassium borohydride, the ratio of the sodium borohydride to the potassium borohydride in the mixture is not particularly limited, and the mixture may be a mixture in any ratio.
In the invention, the borohydride is preferably used in the form of a borohydride solution, the molar concentration of the borohydride solution is preferably 0.1-1 mol/L, and more preferably 0.1-0.5 mol/L, the concentration of the borohydride solution cannot be too high, and when the concentration is too high, agglomeration occurs when the material is synthesized, so that the adsorption effect is influenced.
According to the invention, the borohydride solution is preferably dripped into the microbial reductant at a dripping speed of preferably 2-5 mL/min, more preferably 2-3 mL/min, and most preferably 2 mL/min. The invention aims to ensure that the borohydride slowly reacts with iron and sulfur elements by strictly controlling the concentration and the dropping speed of the borohydride solution, and prevents reaction products from agglomerating due to violent reaction speed, thereby influencing the subsequent adsorption effect.
In the present invention, BH in said borohydride4 -The ratio of the iron element in the ferrite to the iron element in the ferrite is preferably 2-4: 1, and more preferably 3: 1.
In the invention, the temperature of the chemical reduction reaction is preferably room temperature, no additional heating or cooling is needed, and the time is preferably 30-90 min, and more preferably 60 min.
In the present invention, the inert gas atmosphere is preferably a nitrogen atmosphere.
After the chemical reduction reaction is finished, the obtained chemical reduction product is preferably subjected to centrifugation, washing and vacuum freeze drying in sequence to obtain the biological zero-valent iron sulfide material.
The present invention is not particularly limited to the specific manner of centrifugation and washing, and may be performed in a manner known to those skilled in the art.
In the invention, the temperature of the vacuum freeze drying is preferably-30 ℃ to-35 ℃, the absolute pressure is preferably 4-7 Pa, and the time of the vacuum freeze drying is not particularly limited.
Taking borohydride as an example, the reaction mechanism for preparing the biological zero-valent iron sulfide material is as follows:
Fe2++2BH4 -+6H2O→Fe0(s)+2B(OH)3+7H2
Fe2++S2-→FeS(s)
the invention provides the biological type zero-valent iron sulfide material prepared by the preparation method in the technical scheme, wherein the aperture of the biological type zero-valent iron sulfide material is 20-60 nm, and the specific surface area is 150-400 m2The porosity is 40-60 percent.
The invention also provides application of the biological zero-valent iron sulfide material in the technical scheme in repairing heavy metal contaminated soil and water. The present invention is not particularly limited in the kind of the heavy metal, and may be applied to any heavy metal known in the art.
In the present invention, the heavy metal preferably includes one or more of Pb, Cu, Zn, and Cd.
The invention is not particularly limited to the specific manner of use described, as such may be readily adapted by those skilled in the art.
In the invention, when the biological zero-valent iron sulfide material is used for repairing heavy metal contaminated soil, the biological zero-valent iron sulfide material is preferably added into the heavy metal contaminated soil at a ratio of 1 kg/t; when the biological zero-valent iron sulfide material is used for repairing heavy metal polluted water, the adding amount of the biological zero-valent iron sulfide material is preferably 1 g/L.
The biological zero-valent iron sulfide material provided by the invention and the preparation method and application thereof are explained in detail by combining the following examples, but the biological zero-valent iron sulfide material cannot be understood as limiting the protection scope of the invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
FIG. 1 is a schematic view of the process flow for preparing a biological zero-valent iron sulfide material in example 1 of the present invention.
A biological type zero-valent iron sulfide material is prepared by the following specific steps:
(1) preparing an improved Baar's culture medium, wherein the formula is as follows: KH (Perkin Elmer)2PO40.5 g/L，NH4Cl 1g/L，CaSO4·2H2O 1g/L，MgSO42g/L, 5g/L sodium citrate, 3.5g/L sodium lactate and 1g/L yeast extract; adjusting the pH value to 7.5; adding kaolin, and controlling the liquid-solid ratio to be 100: 1; filling the solution into an anaerobic bottle, and sterilizing at 121 ℃ for 15 minutes; after the anaerobic bottle is cooled, Fe (NH) after filtration and sterilization is added4)2·(SO4)2·6H2O to 2g/L, inoculating sulfate reducing bacteria in an anaerobic culture box, wherein the initial bacteria concentration is 5 x 107CFU/mL; sealing to ensure that the interior of the anaerobic bottle is in an anaerobic environment, and culturing in a constant temperature oscillator at 30 ℃;
(2) preparing a potassium borohydride solution, wherein the molar concentration of the potassium borohydride is 0.3 mol/L;
(3) after the microorganism in the step (1) is cultured for 72 hours, slowly adding the microorganism into the culture solution at room temperature under the protection of nitrogen atmosphereDripping the potassium borohydride solution prepared in the step (2) at the flow rate of 2mL/min to control BH4 -And the mol ratio of Fe to Fe is 3:1, continuously oscillating for 60min, centrifuging after the reaction is completed, repeatedly washing with ultrapure water, and carrying out vacuum freeze drying (-30 ℃, 7 Pa absolute) to obtain the biological type zero-valent iron sulfide material.
The surface morphology of the prepared biological zero-valent iron sulfide is analyzed by a scanning electron microscope, and the result shows that the prepared biological zero-valent iron sulfide material has rough particle morphology and is in an irregular spherical shape, most fine particles can form aggregates, and the Scanning Electron Microscope (SEM) spectrogram of the biological zero-valent iron sulfide is shown in figure 2. The aperture of the prepared biological type sulfuration zero-valent iron material is 27.146nm, and the specific surface area is 352.691m2In terms of a/g, the porosity was 58.62%.
Example 2
A biological type zero-valent iron sulfide material is prepared by the following specific steps:
(1) preparing an improved ear's culture medium, wherein the formula of the improved ear's culture medium is the same as that in example 1; adjusting the pH value to 7.5; adding kaolin, and controlling the liquid-solid ratio to be 100: 0.5; filling the solution into an anaerobic bottle, and sterilizing at 121 ℃ for 15 minutes; after the anaerobic bottle is cooled, Fe (NH) after filtration and sterilization is added4)2·(SO4)2·6H2O to 3g/L, inoculating sulfate reducing bacteria in an anaerobic culture box, wherein the initial bacteria concentration is 1 x 107CFU/mL; sealing to ensure that the interior of the anaerobic bottle is in an anaerobic environment, and culturing in a constant temperature oscillator at 30 ℃;
(2) preparing a potassium borohydride solution, wherein the molar concentration of the potassium borohydride is 1 mol/L;
(3) after the microorganism in the step (1) is cultured for 72 hours, slowly dripping the potassium borohydride solution prepared in the step (2) into the bacteria culture solution at the flow rate of 5mL/min at room temperature under the protection of nitrogen atmosphere, and controlling BH4 -The mol ratio of Fe/Fe is 4, the mixture is continuously shaken for 60min, after the reaction is completed, the mixture is centrifuged, and is repeatedly washed by ultrapure water, and the biological type zero-valent iron sulfide material is obtained after vacuum freeze drying (-35 ℃ and 4 Pa absolute).
The biotype produced is vulcanizedThe aperture of the zero-valent iron material is 28.153nm, and the specific surface area is 304.156m2In terms of a/g, the porosity was 54.27%.
Example 3
A biological type zero-valent iron sulfide material is prepared by the following specific steps:
(1) preparing an improved ear's culture medium, wherein the formula of the improved ear's culture medium is the same as that in example 1; adjusting the pH value to 7.5; adding kaolin, and controlling the liquid-solid ratio to be 100: 3; filling the solution into an anaerobic bottle, and sterilizing at 121 ℃ for 20 minutes; after the anaerobic bottle is cooled, Fe (NH) after filtration and sterilization is added4)2·(SO4)2·6H2O to 1g/L, inoculating sulfate reducing bacteria in an anaerobic culture box, wherein the initial bacteria concentration is 5 x 107CFU/mL; sealing to ensure that the interior of the anaerobic bottle is in an anaerobic environment, and culturing in a constant temperature oscillator at 30 ℃;
(2) preparing a potassium borohydride solution, wherein the molar concentration of the potassium borohydride is 0.2 mol/L;
(3) after the microorganism in the step (1) is cultured for 72 hours, slowly dripping the potassium borohydride solution prepared in the step (2) into the bacteria culture solution at the flow rate of 5mL/min at room temperature under the protection of nitrogen atmosphere, and controlling BH4 -The mol ratio of Fe/Fe is 2, the mixture is continuously shaken for 60min, the mixture is centrifuged after the reaction is completed, and the mixture is repeatedly washed by ultrapure water and is frozen and dried in vacuum (-30 ℃ and 4 Pa absolute) to obtain the biological type zero-valent iron sulfide material.
The aperture of the prepared biological type sulfuration zero-valent iron material is 34.125nm, and the specific surface area is 293.842m2In terms of a/g, the porosity was 50.63%.
Example 4
A biological type zero-valent iron sulfide material is prepared by the following specific steps:
(1) preparing an improved ear's culture medium, wherein the formula of the improved ear's culture medium is the same as that in example 1; adjusting the pH value to 5; adding kaolin, and controlling the liquid-solid ratio to be 100: 1; filling the solution into an anaerobic bottle, and sterilizing at 121 ℃ for 20 minutes; after the anaerobic bottle is cooled, Fe (NH) after filtration and sterilization is added4)2·(SO4)2·6H2The content of O is up to 2g/L,inoculating sulfate reducing bacteria in an anaerobic culture box, wherein the initial bacteria concentration is 10 multiplied by 107CFU/mL; sealing to ensure that the interior of the anaerobic bottle is in an anaerobic environment, and culturing in a constant temperature oscillator at 30 ℃;
(2) preparing a potassium borohydride solution, wherein the molar concentration of the potassium borohydride is 0.3 mol/L;
(3) after the microorganism in the step (1) is cultured for 72 hours, slowly dripping the potassium borohydride solution prepared in the step (2) into the bacteria culture solution at the flow rate of 2mL/min at room temperature under the protection of nitrogen atmosphere, and controlling BH4 -And the mol ratio of Fe to Fe is 4, continuously oscillating for 90min, centrifuging after the reaction is completed, repeatedly washing with ultrapure water, and carrying out vacuum freeze drying (-35 ℃, the absolute pressure is 4 Pa) to obtain the biological type zero-valent iron sulfide material.
The aperture of the prepared biological type sulfuration zero-valent iron material is 26.862nm, and the specific surface area is 346.514m2In terms of a/g, the porosity was 55.71%.
Example 5
A biological type zero-valent iron sulfide material is prepared by the following specific steps:
(1) preparing a modified ear's culture medium, wherein the formula of the modified ear's culture medium is the same as that of example 1; adjusting the pH value to 7.5; adding white carbon black, and controlling the liquid-solid ratio to be 100: 2; filling the solution into an anaerobic bottle, and sterilizing at 121 ℃ for 20 minutes; after the anaerobic bottle is cooled, Fe (NH) after filtration and sterilization is added4)2·(SO4)2·6H2O to 3g/L, inoculating sulfate reducing bacteria in an anaerobic culture box, wherein the initial bacteria concentration is 5 x 107CFU/mL; sealing to ensure that the interior of the anaerobic bottle is in an anaerobic environment, and culturing in a constant temperature oscillator at 30 ℃;
(2) preparing a potassium borohydride solution, wherein the molar concentration of the potassium borohydride is 2 mol/L;
(3) after the microorganism in the step (1) is cultured for 60 hours, slowly dripping the potassium borohydride solution prepared in the step (2) into the bacteria culture solution at the flow rate of 5mL/min at room temperature under the protection of nitrogen atmosphere, and controlling BH4 -The mol ratio of Fe to Fe is 4, the mixture is continuously shaken for 60min, after the reaction is completed, the mixture is centrifuged, and ultrapure water is used for reactionAnd (4) washing again, and performing vacuum freeze drying at (-30 ℃ and 4 Pa absolute) to obtain the biological type zero-valent iron sulfide material.
The aperture of the prepared biological type sulfuration zero-valent iron material is 22.685nm, and the specific surface area is 202.427m2In terms of a/g, the porosity was 49.54%.
Example 6
A biological type zero-valent iron sulfide material is prepared by the following specific steps:
(1) preparing a modified ear's culture medium, wherein the formula of the modified ear's culture medium is the same as that of example 1; adjusting the pH value to 7.5; adding talcum powder, and controlling the liquid-solid ratio to be 100: 1; filling the solution into an anaerobic bottle, and sterilizing at 121 ℃ for 20 minutes; after the anaerobic bottle is cooled, Fe (NH) after filtration and sterilization is added4)2·(SO4)2·6H2O to 2g/L, inoculating sulfate reducing bacteria in an anaerobic culture box, wherein the initial bacteria concentration is 5 x 107CFU/mL; sealing to ensure that the interior of the anaerobic bottle is in an anaerobic environment, and culturing in a constant temperature oscillator at 30 ℃;
(2) preparing a potassium borohydride solution, wherein the molar concentration of the potassium borohydride is 1 mol/L;
(3) and (2) after the microorganisms in the step (1) are cultured for 72 hours, slowly dripping the potassium borohydride solution prepared in the step (2) into the bacteria culture solution at the flow rate of 5mL/min under the protection of nitrogen atmosphere at room temperature, continuously shaking for 90min, centrifuging after the reaction is completed, repeatedly washing with ultrapure water, and carrying out vacuum freeze drying (-35 ℃, and the absolute pressure of 4 Pa) to obtain the biological zero-valent iron sulfide material.
The aperture of the prepared biological type sulfuration zero-valent iron material is 29.564nm, and the specific surface area is 293.651m2In terms of a/g, the porosity was 55.47%.
Comparative example 1
The kaolin is directly used for repairing heavy metal polluted soil and water.
Comparative example 2
(1) Preparing an improved ear's culture medium, wherein the formula of the improved ear's culture medium is the same as that in example 1; adjusting the pH value to 7.5; adding kaolin, and controlling the liquid-solid ratio to be 100: 1; loading the solution into anaerobic bottle at 121 deg.CSterilizing for 20 minutes; after the anaerobic bottle is cooled, Fe (NH) after filtration and sterilization is added4)2·(SO4)2·6H2O to 1g/L, inoculating sulfate reducing bacteria in an anaerobic culture box, wherein the initial bacteria concentration is 10 multiplied by 107CFU/mL; sealing to ensure that the interior of the anaerobic bottle is in an anaerobic environment, and culturing in a constant temperature oscillator at 30 ℃;
(2) and (2) after the microorganism in the step (1) is cultured for 72 hours, centrifuging, and carrying out vacuum freeze drying at (-35 ℃ and 4 Pa absolute pressure) to obtain the biological type zero-valent iron sulfide material.
Comparative example 3
(1) Preparing a modified ear's culture medium, wherein the formula of the modified ear's culture medium is the same as that of example 1; adjusting the pH value to 7.5; adding kaolin, and controlling the liquid-solid ratio to be 100: 1; adding Fe (NH)4)2·(SO4)2·6H2O is 3 g/L; sealing to ensure that the interior of the anaerobic bottle is in an anaerobic environment, and placing the anaerobic bottle in a constant temperature oscillator to oscillate at the temperature of 30 ℃;
(2) preparing a potassium borohydride solution, wherein the molar concentration of the potassium borohydride is 0.5 mol/L;
(3) after the solution in the step (1) is vibrated for 72 hours, slowly dripping the potassium borohydride solution prepared in the step (2) into the bacterium culture solution at the flow rate of 2mL/min at room temperature under the protection of nitrogen atmosphere, and controlling BH4 -The mol ratio of Fe/Fe is 4, the mixture is continuously shaken for 60min, after the reaction is completed, the mixture is centrifuged, and the mixture is repeatedly washed by ultrapure water and is frozen and dried in vacuum (-35 ℃ and 4 Pa absolute), thus obtaining the non-biological type zero-valent iron sulfide material.
Performance test 1:
taking the polluted soil around a certain lead-zinc coal mine area in Henan Heyang as a sample, air-drying the sample, sieving the sample by a 1mm sieve, adding the materials obtained in the examples 1-6 and the comparative examples 1-3 into the heavy metal polluted soil according to the proportion of 1 wt%, uniformly mixing, performing under a flooding condition, and meanwhile, setting a blank control experiment group without adding the materials. And after 20 days of maintenance, a soil toxicity leaching experiment is carried out by adopting a sulfuric acid-nitric acid method (HJ/T299-2007). The detection results of the heavy metal content before and after the repair are shown in the following table 1.
TABLE 1 heavy metal content before and after remediation
Figure BDA0002987847950000111
Figure BDA0002987847950000121
As can be seen from the above table 1, the biological zero-valent iron sulfide material prepared by the invention is used for repairing lead, copper, zinc and cadmium composite contaminated soil, and can significantly reduce the concentration of heavy metals in the soil leachate. Compared with a comparative example, the biological zero-valent iron sulfide material has a stabilizing rate to heavy metal which is obviously better than that of a non-biological zero-valent iron sulfide material. The effect of example 1 is best compared with the other examples, with the soil having a lead stabilization rate of 93.51%, a copper stabilization rate of 97.01%, a zinc stabilization rate of 95.52%, and a cadmium stabilization rate of 86.96% after 20 days.
Performance detection 2:
taking the mine pit wastewater of a certain lead-zinc coal mine area in Henan Heyang as a sample (the lead concentration is 5.41mg/L, the copper concentration is 3.35mg/L, the zinc concentration is 26.58mg/L, and the cadmium concentration is 1.64mg/L before restoration). Adding the materials obtained in the examples 1-6 and the comparative examples 1-3, controlling the adding amount to be 1g/L, continuously oscillating for 10h, filtering, detecting the concentration of the heavy metal in the solution by adopting an ICP-AES inductively coupled atomic emission spectrometer, and detecting the heavy metal content before and after repairing as shown in the following table 2. The results of multiple parallel experiments show that the remediation effect of example 5 is the best (Table 2), and the lead concentration, the copper concentration, the zinc concentration and the cadmium concentration in the treated wastewater are respectively less than 0.01mg/L, 0.003mg/L, 0.004mg/L and 0.001 mg/L. After the repair, the heavy metals can stably reach the I-type standard of the national Integrated wastewater discharge Standard (GB8978-1996) and the environmental quality Standard of surface Water (GB 3838-.
TABLE 2 heavy metal content before and after remediation
Figure BDA0002987847950000122
Figure BDA0002987847950000131
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 (7)

1. A preparation method of a biological type zero-valent iron sulfide material is characterized by comprising the following steps:
adding the template material into a sulfate reducing bacteria culture medium, and carrying out anaerobic sterilization to obtain a sterilized culture solution;
mixing the sterilized culture solution with ferrous salt, inoculating sulfate reducing bacteria, and carrying out microbial reduction in an anaerobic environment to obtain a microbial reduced matter; the ferrous salt is FeSO4·7H2O and/or Fe (NH)4)2·(SO4)2·6H2O; the mixed solution obtained after the sterilization culture solution and the ferrous salt are mixed contains Fe2+The concentration of (A) is 0.14-0.5 g/L;
mixing the microbial reductant and a reducing agent in an inert gas atmosphere to carry out chemical reduction reaction to obtain the biological zero-valent iron sulfide material; the reducing agent is borohydride, the borohydride is used in the form of borohydride solution, and the molar concentration of the borohydride solution is 0.1-1 mol/L.
2. The method according to claim 1, wherein the sulfate-reducing bacteria culture medium comprises the following components in the following concentrations: KH (Perkin Elmer)2PO4 0.5±0.05g/L，NH4Cl 1±0.05g/L，CaSO4·2H2O 1±0.05g/L，MgSO4 2 plus or minus 0.1g/L, 5 plus or minus 0.1g/L sodium citrate, 3.5 plus or minus 0.1g/L sodium lactate and 1 plus or minus 0.05g/L yeast extract.
3. The method according to claim 1, wherein the template material comprises one or more of kaolin, talc and white carbon black.
4. The preparation method according to claim 1 or 3, wherein the liquid-solid ratio of the template material added in the sulfate reducing bacteria culture medium is 100: 0.5-3.
5. The method according to claim 1, wherein the sulfate-reducing bacteria are inoculated in the sterilized culture medium in an amount of not less than 1.0X 107CFU/mL。
6. The biotype zero-valent iron sulfide material prepared by the preparation method of any one of claims 1 to 5, wherein the biotype zero-valent iron sulfide material has a pore diameter of 20 to 60nm and a specific surface area of 150 to 400m2The porosity is 40-60 percent.
7. The use of the biological zero-valent iron sulfide material of claim 6 in the remediation of heavy metal contaminated soils and water.
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