CN110642324B - Method for removing antimony in wastewater - Google Patents
Method for removing antimony in wastewater Download PDFInfo
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- CN110642324B CN110642324B CN201910756385.7A CN201910756385A CN110642324B CN 110642324 B CN110642324 B CN 110642324B CN 201910756385 A CN201910756385 A CN 201910756385A CN 110642324 B CN110642324 B CN 110642324B
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- antimony
- iron oxide
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention provides a method for removing antimony in wastewater, belonging to the field of water treatment. The method for removing the antimony in the wastewater takes primary ecological secondary iron oxide as an adsorbent to remove the antimony; the primary ecological secondary iron oxide is iron oxide generated in the acidic wastewater of the coal mine, is in a yellow-brown granular shape, has a pore structure inside, mainly comprises Fe, S, O and H, is an iron sulfate secondary mineral, is non-toxic and harmless, can avoid the problem of secondary pollution caused by an adsorbent, has the adsorption quantity of 219.78mg/g on Sb (III) and 366.30mg/g on Sb (V), can effectively remove antimony ions in the wastewater, is low in cost, changes waste into valuable, accords with the environmental protection strategy of treating waste with waste, and has important social and economic meanings.
Description
Technical Field
The invention belongs to the technical field of water treatment, relates to a method for removing antimony in wastewater, and particularly relates to a method for removing antimony in wastewater by using primary ecological secondary iron oxide.
Background
Antimony (Sb) is a potentially toxic and carcinogenic human non-essential element that has become an "emerging" long-distance transport global environmental pollutant. Antimony and its compounds have wide application, and are mainly used for producing ceramics, glass, electrical appliances, paints, pyrotechnic materials, flame retardants and other aspects. China is the most abundant world country of antimony ore resources, and annual output accounts for 80% of the global market. Antimony has active geochemical properties in the surface environment and is easy to migrate and diffuse in the water environment, and antimony pollution of water bodies in China is becoming serious due to activities of antimony-containing mineral resources such as mining, metallurgy, chemical production, fossil fuel combustion and the like. The concentration of the water is regulated to be not more than 5 mug/L by the surface water environmental quality standard and the sanitary standard of drinking water in China. Therefore, the control and repair of antimony contamination in water bodies face strict requirements and severe challenges. The adsorption method is the most ideal antimony removal method at present because the adsorption method can be suitable for removing low-concentration heavy metal ions, and has the advantages of high efficiency, low cost, easy operation and the like.
Iron-containing adsorption materials are of the greatest interest based on the amphoteric chemistry and strong reactivity of iron, as well as the important role of the redox process of iron in the morphological transformation and adsorption/immobilization behavior of heavy metal ions. At present, common iron oxides include goethite, lepidocrocite, ferrihydrite, hematite modified magnetic nanoparticles, ferrate and composite oxides of iron and other heavy metals such as manganese, although researches prove that the iron oxide materials have good adsorption effect on antimony and have higher antimony removal capability than commercial ferroferric oxide and hematite, the antimony removal capability of the iron oxide materials still cannot meet the requirement, in addition, when the composite oxides of iron and other heavy metals are used, the problem of secondary pollution caused by the heavy metals exists, for example, when the iron-manganese composite oxides are used, because of Mn4+Redox action of (3), presence of Mn2+Risk of liberation, and Mn2+Belongs to one of the water quality safety monitoring indexes.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a method for removing antimony in wastewater.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a method for removing antimony in wastewater, which takes primary ecological secondary iron oxide as an adsorbent to remove antimony ions in the wastewater containing antimony; the primary ecological secondary iron oxide is iron oxide newly generated in acid wastewater of a coal mine, is yellowish-brown loose particles, has a pore structure inside, is a naturally formed iron sulfate secondary mineral, mainly comprises Fe, S, O and H, and is mainly characterized by comprising Shi mineral, jarosite and goethite, the microscopic morphology of the primary ecological secondary iron oxide is shown in figure 1A, the primary ecological secondary iron oxide is porous spherical or hemispherical with different bulk sizes, is loosely arranged and has obvious structural defect feeling, while the non-mature secondary iron oxide is dense spherical with regular and compact shape, and is a dark yellowish-brown dense iron mineral. The applicant finds that the secondary iron oxides with different maturity have different removal effects on antimony, wherein the removal effect of the primary secondary iron oxides on antimony is very excellent and far better than that of other iron oxides such as schlemite, jarosite, goethite and the like and composite oxides of iron and other heavy metals.
As a preferred embodiment of the process of the present invention, the pH of the antimony-containing waste water is from 2 to 10.
As a preferred embodiment of the method of the invention, when the primary ecological secondary iron oxide is applied to removing Sb (III) in the antimony-containing wastewater, the pH value of the antimony-containing wastewater is 7.
As a preferred embodiment of the method of the invention, when the primary ecological secondary iron oxide is applied to the removal of Sb (V) in the antimony-containing wastewater, the pH value of the antimony-containing wastewater is 3.
As a preferred embodiment of the method of the invention, the time taken for removing the antimony ions in the antimony-containing wastewater by the primary ecological secondary iron oxide does not exceed 12 hours.
As a preferred embodiment of the method, the time for removing the antimony ions in the antimony-containing wastewater by the primary ecological secondary iron oxide is 10-12 hours.
As a preferred embodiment of the method of the invention, the nascent secondary iron oxide is subjected to removal of antimony ions from antimony-containing wastewater at 25-45 ℃.
As a preferred embodiment of the method of the invention, the concentration of antimony ions in the antimony-containing wastewater is less than or equal to 1568 mu g/L.
As a preferred embodiment of the method of the present invention, the ratio of said primary ecological secondary iron oxide to said antimony-containing wastewater is 1 mg: 4 mL.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method for removing the antimony in the wastewater can effectively remove the antimony ions in the wastewater, and the adsorption amount of the adopted primary ecological secondary iron oxide on the Sb (III) is 219.78mg/g, and the adsorption amount on the Sb (V) is 366.30 mg/g.
(2) The primary ecological secondary iron oxide adsorbent adopted by the method for removing the antimony in the wastewater mainly comprises Fe, S, O and H, is an iron sulfate secondary mineral, is non-toxic and harmless, and avoids the problem of secondary pollution caused by the adsorbent.
(3) The primary ecological secondary iron oxide adsorbent adopted by the method for removing the antimony in the wastewater is a naturally formed product, and compared with the iron oxide adsorbent synthesized by commercial ferrite at present, the cost is low.
(4) The primary ecological secondary iron oxide adopted by the method for removing antimony in wastewater is collected from the acidic wastewater of the coal mine, and is applied to removing antimony ions in the wastewater, so that the waste recycling is realized, the environmental protection strategy of treating waste with waste is met, and the method has important social and economic significance.
Drawings
FIG. 1 is a micro-topography of nascent (Panel A) and mature (Panel B) secondary iron oxides;
FIG. 2 is a graph comparing the adsorption capacity of different antimony removing materials for antimony;
FIG. 3 is a graph showing the relationship between the pH of the solution and the antimony removal performance of the primary ecological secondary iron oxide used in the present invention;
FIG. 4 is a graph showing the relationship between adsorption time and antimony removal performance of nascent iron oxide used in the present invention;
FIG. 5 is a graph showing the relationship between the adsorption temperature and the antimony removal performance of nascent iron oxide used in the present invention;
FIG. 6 is a graph showing the effect of the primary ecological secondary iron oxide used in the present invention in removing antimony from the actual wastewater.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Examples
One embodiment of the method for removing antimony in wastewater of the invention comprises the following steps: collecting primary ecological secondary iron oxide in a water pit where the acidic wastewater of the coal mine is collected, drying and grinding the primary ecological secondary iron oxide, adding the primary ecological secondary iron oxide into wastewater containing Sb (III) and/or Sb (V) with the pH value of 2-10, oscillating the wastewater at the temperature of 25-45 ℃ for no more than 12 hours, and then carrying out solid-liquid separation to remove antimony ions in the wastewater.
The applicant researches the antimony removal performance of primary ecological secondary iron oxide, the primary ecological secondary iron oxide adopted in the research is formed by coal mine acid wastewater under natural conditions, the concentrations of iron ions and sulfate ions in the acid wastewater are 920 and 4905mg/L respectively, and the pH value of a solution is 2.0-2.7. The acid wastewater is collected in a water pit, and primary secondary iron oxide is generated under the action of microorganisms such as sulfate reducing bacteria and the like and oxygen. Collecting primary ecological secondary iron oxide in the water pit, drying at room temperature, grinding, and sieving with 80 mesh sieve.
(1) Comparison of the antimony removal effect of the primary ecological secondary iron oxide with that of other antimony removal materials
Preparing a Sb (III) solution with the Sb (III) concentration of 75mg/L, preparing a Sb (V) solution with the Sb (V) concentration of 75mg/L, and preparing the Sb (III) solution according to the proportion of primary ecological secondary iron oxides: different iron oxides were added to the above solutions at a ratio of 5mg to 20mL, and then shaken at 25 ℃ for 12 hours, followed by solid-liquid separation to obtain adsorbed solutions, and the concentration of Sb (iii) or Sb (v) in the adsorbed solutions was measured. The antimony removal effect of the primary ecological secondary iron oxide and other reported antimony removal materials used in the invention is counted, and the specific result is shown in figure 2.
As can be seen from FIG. 2, the antimony removal effect of the primary ecological secondary iron oxide is far better than that of MnO2Nanofiber, alpha-FeOOH, beta-FeOOH, alpha-Fe2O3Cerium doped Fe3O4The composite material comprises a synthesized Shi mineral, bentonite, a ferro-manganese composite oxide, amorphous ferrihydrite and a graphene composite Shi mineral.
(2) Effect of pH on antimony removal from nascent Secondary iron oxides
Respectively adding 5mg of primary ecological secondary iron oxide into 20mL of Sb (III) solutions with different pH values and Sb (III) concentration of 75mg/L, respectively adding 5mg of primary ecological secondary iron oxide into 20mL of Sb (V) solutions with different pH values and Sb (V) concentration of 75mg/L, respectively oscillating for 12h at 25 ℃, then carrying out solid-liquid separation to obtain adsorbed solutions, measuring the concentration of Sb (III) or Sb (V) in the adsorbed solutions, and counting the results, wherein the specific results are shown in figure 3.
(3) Influence of adsorption time on antimony removal effect of primary ecological secondary iron oxide
Respectively adding 5mg of primary ecological secondary iron oxide into 20mL of solutions with pH values of 3 and 7, wherein the solutions respectively contain 75mg/L of Sb (III) and Sb (V), then respectively oscillating at 25 ℃ for 0-12 h, then carrying out solid-liquid separation to obtain adsorbed solutions, measuring the concentrations of Sb (III) and Sb (V) in the adsorbed solutions, and counting the results, wherein the results are shown in figure 4 specifically.
(4) Influence of adsorption temperature on antimony removal effect of nascent state secondary iron oxide
Respectively adding 5mg of primary ecological secondary iron oxide into 20mL of solution with the pH value of 7, wherein the solution contains Sb (III) and Sb (V) with the concentration of 75mg/L, oscillating at 25 ℃, 35 ℃ and 45 ℃ for 12h, performing solid-liquid separation to obtain adsorbed solution, measuring the concentrations of Sb (III) and Sb (V) in the adsorbed solution, and counting the results, wherein the results are shown in figure 5.
(5) Antimony removal effect of primary ecological secondary iron oxide on actual antimony-containing wastewater
Taking 5 industrial wastewater samples with actual antimony concentration of 19.8-1568 mu g/L, and respectively preparing the following raw materials according to the proportion of primary ecological secondary iron oxide: waste water 5mg: adding 20mL of primary ecological secondary iron oxide into the 5 water samples, oscillating at 25 ℃ for 12h respectively, performing solid-liquid separation to obtain a solution after adsorption, measuring the concentration of Sb (III) or Sb (V) in the solution after adsorption, and counting the result, wherein the specific result is shown in FIG. 6.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A method for removing antimony in wastewater is characterized by comprising the following steps: the method takes primary ecological secondary iron oxide as an adsorbent to remove antimony ions in the antimony-containing wastewater with the pH value of 2-10; the primary ecological secondary iron oxide is iron oxide generated in the acid wastewater of the coal mine, is in a yellow brown granular shape, has a pore structure inside, has a microstructure which is in a loose arrangement and is in a porous spherical shape or a hemispherical shape with different sizes, mainly comprises Fe, S, O and H, is a naturally formed iron sulfate secondary mineral, and is mainly characterized by comprising schlempe mineral, jarosite and goethite; the primary ecological secondary iron oxide is collected in a water pit where the coal mine acidic wastewater is collected, and the primary ecological secondary iron oxide is collected in the water pit and naturally generated under the action of sulfate reducing bacteria and oxygen; the concentrations of iron ions and sulfate ions in the coal mine acid wastewater are 920 and 4905mg/L respectively, and the pH value is 2.0-2.7.
2. The method of claim 1, wherein: when the primary ecological secondary iron oxide is applied to removing Sb (III) in the antimony-containing wastewater, the pH value of the antimony-containing wastewater is 7.
3. The method of claim 1, wherein: when the primary ecological secondary iron oxide is applied to removing Sb (V) in the antimony-containing wastewater, the pH value of the antimony-containing wastewater is 3.
4. The method of claim 1, wherein: the time for removing the antimony ions in the antimony-containing wastewater by the primary ecological secondary iron oxide is not more than 12 hours.
5. The method of claim 4, wherein: the time for removing the antimony ions in the antimony-containing wastewater by the primary ecological secondary iron oxide is 10-12 hours.
6. The method of claim 1, wherein: and removing antimony ions in the antimony-containing wastewater by using the nascent-state secondary iron oxide at 25-45 ℃.
7. The method of claim 1, wherein: the concentration of antimony ions in the antimony-containing wastewater is less than or equal to 1568 mu g/L.
8. The method of claim 1, wherein: the proportion of the primary ecological secondary iron oxide to the antimony-containing wastewater is 1 mg: 4 mL.
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| CN113149125A (en) * | 2021-04-16 | 2021-07-23 | 四川省农业科学院土壤肥料研究所 | Method for removing antimony pollutants in water |
| CN113441538A (en) * | 2021-06-25 | 2021-09-28 | 中国科学院沈阳应用生态研究所 | Sulfur-induced stabilization treatment method for iron-rich antimony-polluted soil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910466A (en) * | 2014-02-28 | 2014-07-09 | 南京农业大学 | Method for high-efficiency precipitation of soluble iron in acid mine drainage |
| CN105381780A (en) * | 2015-12-07 | 2016-03-09 | 中国科学院生态环境研究中心 | Magnetic absorbent for removing arsenic and antimony through adsorption-superconducting magnetic separating and preparation method thereof |
| CN110064357A (en) * | 2019-04-04 | 2019-07-30 | 浙江大学 | Efficiently except the preparation method of antimony adsorbent and its application in treatment of dyeing wastewater |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910466A (en) * | 2014-02-28 | 2014-07-09 | 南京农业大学 | Method for high-efficiency precipitation of soluble iron in acid mine drainage |
| CN105381780A (en) * | 2015-12-07 | 2016-03-09 | 中国科学院生态环境研究中心 | Magnetic absorbent for removing arsenic and antimony through adsorption-superconducting magnetic separating and preparation method thereof |
| CN110064357A (en) * | 2019-04-04 | 2019-07-30 | 浙江大学 | Efficiently except the preparation method of antimony adsorbent and its application in treatment of dyeing wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 《酸性矿山废水中生物成因次生高铁矿物的形成及环境工程意义》;周立祥;《地学前缘（中国地质大学（北京）：北京大学）》;20081130;第15卷(第6期);第74-75页摘要，第75-76页第1节 * |
| 《针铁矿吸附去除水中锑特性研究》;刘淑琳 等;《四川环境》;20180430;第37卷(第2期);第13页摘要，第16页第2.3节，图7 * |
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