CN113480030A - Method for removing hexavalent chromium and/or organic matters - Google Patents

Method for removing hexavalent chromium and/or organic matters Download PDF

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CN113480030A
CN113480030A CN202110479182.5A CN202110479182A CN113480030A CN 113480030 A CN113480030 A CN 113480030A CN 202110479182 A CN202110479182 A CN 202110479182A CN 113480030 A CN113480030 A CN 113480030A
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hexavalent chromium
fes
persulfate
organic matters
phenol
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CN113480030B (en
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杨卫春
李晓敏
李琦
杨志辉
张晓明
廖骐
石岩
郑钧浩
姜智
熊子璇
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Central South University
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    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • 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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Soil Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Removal Of Specific Substances (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention provides a method for removing hexavalent chromium and/or organic matters. The invention adopts a ball milling composite material (FeS) of pyrite and iron powder2/Fe0) Taking persulfate as an oxidant as a reducing agent and a catalyst to construct FeS2/Fe0The PS composite system realizes the quick and synergistic removal of organic matters and hexavalent chromium. The method is beneficial to greatly improving the oxidative degradation rate of the organic matters and the reduction rate of hexavalent chromium, and the removal efficiency of the organic matters and the reduction rate of hexavalent chromium can reach 100% in a short time. The invention reduces the processing cost and has larger practical application value. The method is simple to operate and remarkable in effect, and provides green and efficient remediation and treatment for industrial organic-heavy metal combined polluted wastewater and soilThe new direction.

Description

Method for removing hexavalent chromium and/or organic matters
Technical Field
The invention belongs to the field of heavy metal complex wastewater treatment and site remediation, and particularly relates to a method for removing organic matters and/or hexavalent chromium.
Background
With the development of industries such as tanning, electroplating, printing and dyeing, textile and the like, high-toxicity Cr (VI) and organic pollutants (such as phenol) widely exist in waste water and actual environment, and the composite pollution causes more serious harm to the environment and human beings due to the comprehensive toxicity of the composite pollution. The two common oxidation states of chromium, primarily in the environment, are (cr (iii) and cr (vi)). Chromium in the form of cr (vi) is one of the most notorious pollutants and is characterized by strong toxicity, carcinogenicity, mobility, and one hundred times higher toxicity than cr (iii), and is therefore of greater environmental concern. In addition, toxic organic compounds mainly containing phenols are discharged into receiving water, and negative effects are brought to the society. The world health organization allows the maximum concentration of the phenolic substances discharged in the water body to be 1 mug/L.
The restoration difficulty is high due to the pollution characteristic of coexistence of organic matters and hexavalent chromium. The main method for removing hexavalent chromium is a reduction method, i.e. hexavalent chromium in a high toxicity state is reduced into trivalent chromium, and phenol removal is mainly through oxidative degradation (such as advanced oxidation). Under the same system, the oxidation degradation of organic pollutants is difficult to realize under the condition of reducing hexavalent chromium, and active ingredients for the oxidation degradation of the organic pollutants possibly cause trivalent chromium to be oxidized into hexavalent chromium with stronger toxicity.
At present, researchers research the synergistic removal of hexavalent chromium and phenol by homogeneous and heterogeneous photocatalytic oxidation, but photocatalysts often have photo-corrosivity and instability, and hexavalent chromium may not be completely reduced and thus cannot reach the standard emission level.
Disclosure of Invention
The invention aims to construct a method for removing organic matters and hexavalent chromium composite pollution in wastewater/soil. The method mainly utilizes FeS2/Fe0Strong oxidation reduction buffer capacity, can release acid and adjust alkali in the reaction process, maintains the reaction activity, and simultaneously utilizes FeS2/Fe0The released ferrous ions and surface structure ferrous iron catalytically activate persulfate, active substances (such as singlet oxygen and the like) generated by the method have high oxidation selectivity, phenol can be selectively oxidized and degraded without oxidizing trivalent chromium, so that the synergetic removal of hexavalent chromium and phenol is realized, and the method has the characteristics of simple operation, economy, feasibility, high efficiency, environmental friendliness and the like.
The specific technical scheme of the invention is as follows:
a method for removing hexavalent chromium and/or organic substances comprises adding FeS2/Fe0The composite material and persulfate are added into a system containing hexavalent chromium and/or organic matters for reaction.
In the method, the organic matter comprises phenolic organic matter, preferably: at least one of phenol, catechol, and bisphenol A.
Said process, FeS2/Fe0The composite material is prepared by mixing FeS2Mixing the substances with the content of more than 95% with reducing iron powder, adding a chelating agent, fully mixing, taking out after ball milling, and sieving to obtain the product.
Further, the FeS2The substance with content of more than 95% comprises FeS2The mass fraction of natural pyrite or lead-zinc metal ore dressing tailings, iron powder or industrial scrap iron is more than 95%, and the natural pyrite or lead-zinc metal ore dressing tailings, the iron powder or the industrial scrap iron preferably pass through 20 meshes.
Further, FeS2The molar ratio of the iron powder to the reducing iron powder is 7:3 to 9:1, preferably 8:2 to 9:1, and more preferably 9: 1.
Further, the chelating agent comprises: one or more of citric acid or citrate, preferably one or more of citric acid, calcium citrate and potassium citrate, and the chelating agent is preferably added in an amount of 1-8%, preferably 1-4% and further preferably 1-3% of the total mass fraction of the materials.
Further, the mass ratio of the total materials to the grinding balls is 1:5-1:20, the ball milling rotation speed is 200-.
The method is characterized in that the system containing hexavalent chromium and/or organic matters comprises waste water, waste gas, waste residues or soil containing hexavalent chromium and/or organic matters; the concentration of organic matters in the wastewater is 10-30mg/L, and the concentration of hexavalent chromium is 10-80 mg/L; the concentration ranges of the organic matters and the hexavalent chromium in the waste gas, the waste residue or the soil are 40-50mg/kg and 400-500mg/kg respectively.
The method is that in a liquid reaction system, the FeS2/Fe0The dosage of the composite material is 0.2-1g/L, the persulfate is potassium persulfate or sodium persulfate, preferably potassium persulfate, and the dosage of the persulfate is 0.5-3mM/100 mL;
in a solid reaction system, the FeS2/Fe0The consumption of the composite material is 1% -5% of the waste residue or soil, the persulfate is potassium persulfate or sodium persulfate, preferably potassium persulfate, and the consumption is 4-15mM per 20g of waste residue or soil.
In the method, the pH range of the system containing hexavalent chromium and/or organic matters is 3-10. Especially can treat wastewater or soil with pH value of 7-10.
The invention utilizes FeS2/Fe0The redox buffer capacity is strong, and acid and alkali can be released in the reaction process (figure 3), so that the reactivity is maintained.
The mechanism for simultaneously removing organic matters and hexavalent chromium is as follows:
(1) on one hand, the pyrite is used as a release source of ferrous ions to effectively activate persulfate to form free radicals to participate in efficient degradation of organic matters such as phenol and the like; on the other hand, the ferrous iron and the zero-valent iron released by the material can effectively reduce the hexavalent chromium in the environment, and meanwhile, the oxidation process of the organic matter and the reduction process of the hexavalent chromium can be mutually promoted in the reaction process.
(2) The ferric iron generated in the organic matter degradation and hexavalent chromium reduction processes can be reduced into ferrous iron by pyrite and zero-valent iron so as to participate in pollutant degradation again to form a circulating system.
(3) In FeS2/Fe0Under the action, dissolved oxygen in the reaction system can participate in generating superoxide radicals to generate active oxidation components such as singlet oxygen and the like, and can be mutually converted with sulfate radicals, so that a plurality of active oxidation components can participate in the oxidative degradation of organic matters (phenol) together, the degradation efficiency is greatly improved, and the singlet oxygen of the main active oxidation components in the reaction system has higher selectivity and can selectively oxidize phenol organic pollutants (as shown in figure 1).
(4) The process of phenol degradation is beneficial to promoting the release of sulfate radicals in the system (as shown in figure 2), thereby promoting the corrosion of zero-valent iron and generating surface structure ferrous iron with higher activity.
The invention has the following advantages and beneficial effects:
(1) the natural pyrite, the iron powder and the potassium persulfate are used as raw materials, so that the cost is low, secondary pollution is avoided, and the aim of simultaneously converting two pollutants can be fulfilled.
(2) The reaction system has the advantages of cooperatively treating hexavalent chromium and organic matters, and has higher degradation efficiency than that of a single pollutant.
(3) The pyrite has stronger hydrophobicity, so the disadvantage of non-selective reaction of zero-valent iron can be compensated, and the combination of the two is beneficial to adsorbing organic matters on the surface of the material to participate in the reaction.
(4) The material is added with reduced iron powder on the basis of pyrite to form FeS2/Fe0The composite system is favorable for electron transfer and can greatly improve the conversion capacity of two pollutants.
(5) The combination of the pyrite and the reduced iron powder increases the leaching amount of ferrous iron, which is beneficial to the reduction of hexavalent chromium and the oxidation catalysis of phenol.
(6) The system can achieve the high-efficiency removal of hexavalent chromium and phenol within a wider pH range, and the pH value is reduced in the reaction process (as shown in figure 3), so that the absorption of chromium-iron hydroxide on the surface of the material in the reaction process is avoided.
(7) In the system, various active substances mainly containing singlet oxygen are generated in the process of treating hexavalent chromium and phenol, and because the active substances have high oxidation selectivity, the reoxidation of trivalent chromium by strong oxidative free radicals is avoided.
Drawings
FIG. 1 FeS of the invention2/Fe0Identification of free radicals in a reaction system of + PS + phenol + Cr (VI);
FIG. 2 release of sulfate in different systems;
FIG. 3 changes in pH during the reaction of the present invention;
FIG. 4 FeS at different doses2/Fe0+ PS removes hexavalent chromium of low concentration;
FIG. 5FeS2/Fe0+ removing hexavalent chromium with different high concentrations in the composite pollution by a PS system;
FIG. 6 FeS at different doses2/Fe0+ PS para-phenol removal;
FIG. 7 comparison of hexavalent chromium removal for different systems;
FIG. 8 comparison of phenol removal for different systems;
FIG. 9 removal of hexavalent chromium from soil with different potassium persulfate dosages;
FIG. 10 removal of phenol from soil with different potassium persulfate doses;
FIG. 11 hexavalent chromium removal under the initial pH 10 conditions of the present invention;
figure 12 removal of phenol at initial pH 10 according to the invention.
Detailed Description
The following further describes the specific embodiments of the present invention in combination with the technical solutions. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive effort, shall fall within the scope of the present invention.
FeS in the examples of the invention2/Fe0Preparing a composite material:
example 1
Selection of FeS2Drying, vibrating, grinding and screening the pyrite with the mass fraction of more than 95% through a 20-mesh sieve to obtain pyrite particles; fully mixing pyrite and iron powder (passing through 20 meshes) according to a molar ratio of 9:1, adding citric acid with the total material mass fraction of 1%, putting the mixture into a hard stainless steel ball milling tank, adding grinding balls according to a ball-to-material ratio of 15:1, setting the ball milling speed to be 400 r/min, mechanically milling for 4h, and screening through 100 meshes to obtain the iron-based composite material.
Example 2
Selection of FeS2Drying, vibrating, grinding and screening the pyrite with the mass fraction of more than 95% through a 20-mesh sieve to obtain pyrite particles; fully mixing the pyrite and the iron powder (passing through a 20-mesh sieve) according to a molar ratio of 8:2, adding citric acid with the total material mass fraction of 3%, putting the mixture into a hard stainless steel ball milling tank, adding grinding balls according to a ball-to-material ratio of 10:1, setting the ball milling speed to be 300 r/min, mechanically milling for 6h, and screening through a 100-mesh sieve to obtain the iron-based composite material.
Example 3
Selection of FeS2Drying, vibrating, grinding and screening the pyrite with the mass fraction of more than 95% through a 20-mesh sieve to obtain pyrite particles; fully mixing pyrite and iron powder (passing through 20 meshes) according to a molar ratio of 7:3, adding citric acid with the total material mass fraction of 5%, putting the mixture into a hard stainless steel ball milling tank, adding grinding balls according to a ball-to-material ratio of 8:1, setting the ball milling speed to be 500 r/min, mechanically milling for 3h, and screening through 100 meshes to obtain the iron-based composite material.
Example 4
Simulating the preparation of wastewater containing phenol and hexavalent chromium:
(1) preparing 1000mg/LCr (VI) stock solution: 2.8289g of potassium dichromate dried at 120 ℃ for 2 hours is weighed, completely dissolved in a beaker by deionized water, transferred into a 1000ml volumetric flask, and is subjected to constant volume and uniform shaking for later use.
(2) Preparing 500mg/L of phenol mother liquor: 0.005g of melted phenol is weighed into a small beaker, is fully dissolved by a certain amount of methanol and then is transferred into a 500ml volumetric flask to be constant volume and evenly shaken for standby.
(3) Simulation of phenol and hexavalent chromium containing wastewater: a certain amount of Cr (VI) stock solution and a certain amount of phenol mother liquor are transferred and mixed in a 250ml three-neck round-bottom flask, and 100ml of simulated wastewater containing phenol and hexavalent chromium is prepared.
A method for removing low-concentration hexavalent chromium comprises the following steps:
taking simulated wastewater containing low-concentration hexavalent chromium and phenol, and using deionized water to fix the volume so that the total volume of the reaction is 100 ml. 2mM potassium persulfate and 0.2-1g/L of FeS prepared in example 1 was added2/Fe0The reaction is started. Samples were taken over a specified time to detect residual contaminant concentrations.
The initial cr (vi) concentration was 20mg/L and the initial phenol concentration was 10mg/L, without adjusting the initial pH (pH 5). After the reaction, the sample was taken out by syringe and immediately passed through a 0.45 μm filter to obtain a supernatant. Wherein, the hexavalent chromium is measured by a diphenyl carbonyl dihydrazide spectrophotometry. After reacting for 2 hours as shown in fig. 4, the removal rate of hexavalent chromium reaches 100%.
Example 5
A method for removing high-concentration hexavalent chromium comprises the following steps:
a three-mouth round-bottom flask is adopted as a reaction container, simulated wastewater containing high-concentration hexavalent chromium and phenol is taken, and deionized water is used for constant volume, so that the total volume of the reaction is 100 ml. 2mM potassium persulfate and 0.5g/L of FeS prepared in example 2 were added2/Fe0The reaction is started. Samples were taken over a specified time to detect residual contaminant concentrations.
The initial cr (vi) concentration was 40-80mg/L and the initial phenol concentration was 10mg/L, without adjusting the initial pH (pH 5). After the reaction, the sample was taken out by syringe and immediately passed through a 0.45 μm filter to obtain a supernatant. Wherein, the hexavalent chromium is measured by a diphenyl carbonyl dihydrazide spectrophotometry. After 6 hours of reaction as shown in FIG. 5, the removal rate of hexavalent chromium reaches more than 90%.
Example 6
A method for removing phenol:
a three-mouth round-bottom flask is adopted as a reaction container, simulated wastewater containing phenol and hexavalent chromium is taken, and deionized water is used for constant volume, so that the total volume of the reaction is 100 ml. 2mM of potassium persulfate PS and 0.2-1g/L of FeS prepared in example 1 were added2/Fe0To start to reverseShould be used. Samples were taken over a specified time to detect residual contaminant concentrations.
The initial phenol concentration was 10mg/L and the initial cr (vi) concentration was 20mg/L, without adjusting the initial pH (pH 5). After completion of the reaction, the reaction mixture was sampled by a syringe, and immediately passed through a 0.45 μm filter to obtain a supernatant, and methanol was added to the sample to quench radicals. Wherein the phenol is detected by a high performance liquid chromatography machine. As shown in FIG. 6, the removal rate of phenol reached 100% within 5min of the reaction.
Comparative example 1:
FeS prepared in example 1 was used2/Fe0In the condition that the concentration of Cr (VI) is 20mg/L, FeS is respectively compared2/Fe0、phenol、FeS2/Fe0+PS、FeS2/Fe0+phenol、PS+phenol、FeS2/Fe0The six systems of PS + phenol have the reduction effect on hexavalent chromium. Wherein FeS2/Fe0Was used in an amount of 0.5g/L, PS of 2mM, phenol in an amount of 10mg/L, initial pH 5. As shown in FIG. 7, the FeS under construction2/Fe0In the system of + PS + phenol + Cr (VI), the removal rate of hexavalent chromium is the highest, and reaches 100% within 2 h.
From the above results, it is clear that FeS2/Fe0The effect of the + PS + phenol + Cr (VI) is obviously better than that of FeS2/Fe0+ PS + Cr (VI) indicating FeS2/Fe0The four of PS, phenol and Cr (VI) have no choice but to be lack of choice, and a good synergistic effect is generated.
Comparative example 2:
FeS prepared in example 1 was used2/Fe0FeS was compared with the phenol concentration of 10mg/L2/Fe0+PS、Cr(VI)、FeS2/Fe0、PS+Cr(VI)、FeS2/Fe0+Cr(VI)、FeS2/Fe0The degrading effect of the six systems of + PS + Cr (VI) on phenol. Wherein FeS2/Fe0In an amount of 2mM for 0.5g/L, PS, 20mg/L for hexavalent chromium, and an initial pH of 5. As shown in FIG. 8, the FeS under construction2/Fe0In the system of + PS + phenol + Cr (VI), the removal rate of phenol is the highest and reaches within 5minTo 100%.
From the above results, it is clear that FeS2/Fe0The effect of + PS + phenol + Cr (VI) is better than that of FeS2/Fe0+ PS + phenol, indicating FeS2/Fe0The four of PS, phenol and Cr (VI) have no choice but to be used, and a good synergistic effect is generated.
Example 7
Based on the soil of the actual contaminated site, the initial Cr (VI) concentration in the soil was 446 mg/kg. 20g of contaminated soil was weighed into a conical flask and 1% -5% of the FeS prepared in example 1 was added2/Fe0And 10mM potassium persulfate powder are uniformly stirred, then a certain amount of deionized water is added according to the water-soil ratio of 2:1, the mixture is uniformly stirred again, and then the mixture is subjected to standing treatment. No initial pH adjustment was required (pH 7.31). The hexavalent chromium is measured by a Tessier extraction method and then a diphenylcarbonyldihydrazide spectrophotometric method, and after the reaction is carried out for 3 days, the result shows that the removal rate of the hexavalent chromium is 99%. See table 1. This indicates that the method of the present invention can effectively remove hexavalent chromium from the soil.
TABLE 1
Figure BDA0003048497960000071
Example 8
Based on the soil of the actual polluted site, a certain amount of phenol dissolved in ethanol is uniformly sprayed on the surface of the soil, and then the soil is uniformly mixed and put into a fume hood to volatilize the ethanol, so that the hexavalent chromium-phenol polluted soil is prepared. Wherein the initial Cr (VI) concentration of the soil is 446mg/kg, and the phenol concentration is 45.02 mg/kg.
20g of contaminated soil was weighed into an Erlenmeyer flask and 3% of the FeS prepared in example 3 was added2/Fe04mM-15mM potassium persulfate powder is evenly stirred, and then a certain amount of deionized water is added according to the water-soil ratio of 2:1, and the mixture is evenly stirred and then kept stand. No initial pH adjustment (pH 5) was required. The hexavalent chromium is measured by a Tessier extraction method and then a diphenyl carbonyl dihydrazide spectrophotometric method, and the phenol is extracted by an ultrasonic-oscillation extraction method and then is measured by a liquid chromatograph. The results show the removal rate of hexavalent chromium after 1 day of reaction98% and the maximum phenol removal rate was 86.32%. See fig. 9, 10. This shows that the method of the present invention can effectively remove hexavalent chromium and phenol from the soil.
Example 9
Taking simulated wastewater containing low-concentration hexavalent chromium and phenol, and using deionized water to fix the volume so that the total volume of the reaction is 100 ml. 2mM potassium persulfate and 0.5g/L of FeS prepared in example 1 were added2/Fe0The reaction is started. Samples were taken over a specified time to detect residual contaminant concentrations.
The initial cr (vi) concentration was 20mg/L, the initial phenol concentration was 10mg/L, and the initial pH was adjusted to 10. After the reaction, the sample was taken out by syringe and immediately passed through a 0.45 μm filter to obtain a supernatant. Wherein, the hexavalent chromium is measured by a diphenyl carbonyl dihydrazide spectrophotometry. As shown in fig. 11, the removal rate of hexavalent chromium reaches 100% after reacting for 2.5 h; as shown in FIG. 12, the removal rate of phenol after 1 hour of reaction was 100% after extraction by ultrasonic-shaking extraction and determination by liquid chromatograph.

Claims (10)

1. A method for removing hexavalent chromium and/or organic substances is characterized in that FeS is added2/Fe0The composite material and persulfate are added into a system containing hexavalent chromium and/or organic matters for reaction.
2. The method according to claim 1, characterized in that said organic material comprises phenolic organic materials, preferably: at least one of phenol, catechol and bisphenol A.
3. The method of claim 1, wherein the FeS is2/Fe0The composite material is prepared by mixing FeS2Mixing the substances with the content of more than 95% with reducing iron powder, adding a chelating agent, fully mixing, taking out after ball milling, and sieving to obtain the product.
4. The method of claim 3, wherein said FeS is2The substance with content of more than 95% comprises FeS2Mass fraction greater than95% of natural pyrite or lead-zinc metal dressing tailings, iron powder or industrial scrap iron, preferably 20 meshes.
5. The method of claim 3, wherein FeS2The molar ratio of the iron powder to the reducing iron powder is 7:3 to 9:1, preferably 8:2 to 9:1, and more preferably 9: 1.
6. The method of claim 3, wherein said chelating agent comprises: one or more of citric acid or citrate, preferably one or more of citric acid, calcium citrate and potassium citrate, and the chelating agent is preferably added in an amount of 1-8%, preferably 1-4% and further preferably 1-3% of the total mass fraction of the materials.
7. The method as claimed in claim 3, wherein the mass ratio of the total material to the grinding balls is 1:5-1:20, the ball milling rotation speed is 200 and 500 rpm, the ball milling time is 2-6 hours, and the ball milled is passed through a 100-mesh sieve.
8. The method of claim 1 wherein said system containing hexavalent chromium and/or organics comprises a waste water, waste gas, waste residue, or soil containing hexavalent chromium and/or organics; the concentration of organic matters in the wastewater is 10-30mg/L, and the concentration of hexavalent chromium is 10-80 mg/L; the concentration ranges of the organic matters and the hexavalent chromium in the waste gas, the waste residue or the soil are 40-50mg/kg and 400-500mg/kg respectively.
9. The method of claim 8,
in a liquid reaction system, the FeS2/Fe0The dosage of the composite material is 0.2-1g/L, the persulfate is potassium persulfate or sodium persulfate, preferably potassium persulfate, and the dosage of the persulfate is 0.5-3mM/100 mL;
in a solid reaction system, the FeS2/Fe0The consumption of the composite material is 1% -5% of waste residues or soil, and the persulfate is potassium persulfate or potassium persulfateSodium persulfate, preferably potassium persulfate, in an amount of 4-15mM per 20g of waste residue or soil.
10. The process according to any one of claims 1 to 8, characterized in that the pH of said system containing hexavalent chromium and/or organic substances ranges from 3 to 10.
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CN114345372A (en) * 2021-12-14 2022-04-15 广东环境保护工程职业学院 Sulfur-containing compound and preparation method and application thereof
CN114367530A (en) * 2022-01-04 2022-04-19 上海第二工业大学 Mechanochemical remediation method for heavy metal-POPs (persistent organic pollutants) composite contaminated soil
CN114772652A (en) * 2022-04-18 2022-07-22 华南理工大学 Amorphous ferrous disulfide and preparation method and application thereof

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