Adsorbing material for repairing surface water body polluted by arsenic and antimony, preparation method of adsorbing material and method for treating wastewater containing arsenic and antimony

Abstract

The invention provides an adsorbing material for repairing an arsenic and antimony polluted surface water body, a preparation method of the adsorbing material and a method for treating wastewater containing arsenic and antimony, and relates to the technical field of sewage treatment. According to the preparation method of the adsorbing material for repairing the arsenic and antimony polluted surface water body, provided by the invention, the activated zinc oxide particles are firstly subjected to alkali etching to obtain more active sites, and meanwhile, zinc ions are released; and the released zinc ions and the added lanthanum and iron elements are co-precipitated in the pore channels to form a zinc-iron-lanthanum special double-layer metal hydroxide, so that a core-shell structure is formed, and the core-shell structure has a special metal-hydroxyl group, has an inner sphere complexing effect, and can be used for preparing the composite material. The adsorption selectivity on arsenic and antimony is improved; meanwhile, amido is loaded between layers of the double-layer metal hydroxide, so that the selectivity to arsenic and antimony is further improved.

Description

Technical Field

[0001] The present application relates to the technical field of sewage treatment, and in particular to an adsorption material for repairing arsenic- and antimony-contaminated surface water bodies, a preparation method thereof, and a method for treating arsenic- and antimony-containing wastewater. Background Art

[0002] Arsenic and antimony are common heavy metal pollutants in surface water systems in river basins, which have a significant impact on the ecological environment and the health of residents. The treatment of arsenic and antimony-contaminated surface water bodies needs to be carried out urgently.

[0003] Currently available adsorption materials are targeted at special application scenarios of arsenic and antimony contaminated surface water bodies, but have problems such as small adsorption capacity, high cost, small particle size, and easy clogging. Summary of the Invention

[0004] The purpose of this application is to provide an adsorption material for repairing arsenic and antimony contaminated surface water bodies, a preparation method thereof, and a method for treating arsenic and antimony-containing wastewater, aiming to solve the problems of small adsorption capacity, high cost, small particle size, and easy clogging of existing adsorption materials.

[0005] To achieve the above objectives, the present application provides a method for preparing an adsorption material for repairing arsenic and antimony contaminated surface water, comprising: Mixing and stirring the active zinc oxide particles and the first sodium hydroxide solution to obtain modified active zinc oxide particles; Adding the lanthanum salt, the proline solution and the second sodium hydroxide solution to the modified active zinc oxide particles respectively, and performing a first stirring to form a preparation solution A; Adding iron salt to the prepared solution A, performing a second stirring and allowing to stand to form a prepared solution B; The prepared solution B is filtered, washed, and vacuum-dried to obtain the adsorption material for repairing arsenic- and antimony-contaminated surface water.

[0006] In some embodiments, the particle size of the active zinc oxide particles is 1 mm to 3 mm, the concentration of the first sodium hydroxide solution is 1 mol / L to 3 mol / L; and the mass volume ratio of the active zinc oxide particles to the first sodium hydroxide solution is 1 g: (10-20) mL.

[0007] In some embodiments, the mass percentage concentration of the proline solution is 6% to 10%, and the mass volume ratio of the active zinc oxide particles to the proline solution is 1 g: (10 to 20) mL; And / or, the concentration of the second sodium hydroxide solution is 1 mol / L to 3 mol / L; the mass volume ratio of the modified active zinc oxide particles to the second sodium hydroxide solution is 1 g: (5 to 20) mL.

[0008] In some embodiments, the mass ratio of the iron salt, the modified active zinc oxide particles, and the lanthanum salt is (2-3):1:0.1.

[0009] In some embodiments, the iron salt is ferric chloride and / or ferric sulfate, and the lanthanum salt is lanthanum chloride and / or lanthanum nitrate.

[0010] In some embodiments, at least one of the following conditions is met: A. The time for the first stirring, the second stirring, and the mixed stirring is independently 1 hour to 2 hours; B. The standing time is 2h~5h; C. The pH of the prepared solution A and the prepared solution B are both 10.5 and above; D. the pH of the washed material is neutral; E. The vacuum drying temperature is 80°C to 100°C, and the time is 10h to 12h.

[0011] The present application also provides an adsorption material for repairing surface water bodies contaminated by arsenic and antimony, which is prepared by the above-mentioned method for preparing the adsorption material for repairing surface water bodies contaminated by arsenic and antimony.

[0012] In some embodiments, the adsorption material has a particle size of 1 mm to 3 mm, accounting for greater than or equal to 98 wt %.

[0013] The present application also provides a method for treating arsenic- and antimony-containing wastewater, which uses the above-mentioned adsorption material for repairing arsenic- and antimony-contaminated surface water to treat the arsenic- and antimony-containing wastewater.

[0014] In some embodiments, the adsorption material for repairing arsenic- and antimony-contaminated surface water is mixed with the arsenic- and antimony-containing wastewater; and the treatment is performed at a pH of 6-10.

[0015] Compared with the prior art, the advantages of this application include: The present application provides a method for preparing an adsorption material for repairing surface water bodies contaminated by arsenic and antimony. The active zinc oxide particles are first etched with alkali to obtain more active sites, while releasing zinc ions. This can effectively promote the transfer and diffusion of ions during the material preparation process, and utilize the released zinc ions and the added lanthanum and iron elements to co-precipitate in the pores to form a special double-layer metal hydroxide of zinc, iron and lanthanum, forming a core-shell structure with a special metal-hydroxyl group and an inner sphere complexation effect, thereby improving the adsorption selectivity for arsenic and antimony. At the same time, the double-layer metal hydroxide is loaded with amino groups between the layers, further increasing the selectivity for arsenic and antimony. Compared with other adsorbents on the market, it has a different separation principle. The present application mainly relies on the selective adsorption of the zinc, iron and lanthanum double-layer metal hydroxide and the amino group for the adsorption treatment of heavy metals.

[0016] The adsorption material provided in this application for repairing arsenic and antimony contaminated surface water has a large particle size, is not easy to clog, has good selectivity, has a large adsorption capacity, is good in stability, and does not require frequent regeneration.

[0017] The adsorption material for repairing arsenic and antimony contaminated surface water provided in this application is used to treat arsenic and antimony-containing wastewater. The surface water can meet the surface water environmental quality standards after treatment with high efficiency and low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0019] Figure 1 This is a flow chart of a method for preparing an adsorption material for repairing arsenic and antimony contaminated surface water bodies according to the present application; Figure 2 These are scanning electron microscope photos of the adsorption material for remediation of arsenic and antimony contaminated surface water obtained in Example 1 before and after modification; Figure 3 This is the infrared spectrum of the adsorption material obtained in Example 1 for repairing arsenic and antimony contaminated surface water. DETAILED DESCRIPTION

[0020] As used herein: "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0021] The conjunction "consisting of" excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed, excluding materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim, rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0022] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed alone. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including the range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range.

[0023] In these examples, parts and percentages are by mass unless otherwise indicated.

[0024] "Parts by mass" refers to the basic unit of measurement used to express the mass ratio of multiple components. One part can represent any unit of mass, such as 1g or 2.689g. For example, if we say that the parts by mass of component A are a parts and the parts by mass of component B are b parts, this means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, we could say that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number representing a multiplication factor). It's important to note that, unlike parts by mass, the sum of the parts by mass of all components is not limited to 100 parts.

[0025] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0026] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to. Thus, a feature identified as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, "plurality" means two or more, unless otherwise specifically defined.

[0027] This application provides a method for preparing an adsorption material for repairing arsenic and antimony contaminated surface water. Figure 1 ,include: S100: mixing and stirring the active zinc oxide particles and the first sodium hydroxide solution to obtain modified active zinc oxide particles; S200: adding the lanthanum salt, the proline solution and the second sodium hydroxide solution to the modified active zinc oxide particles respectively, and performing a first stirring to form a prepared solution A; S300: adding iron salt to prepared solution A, performing a second stirring and allowing to stand to form prepared solution B; S400: Filtering, washing, and vacuum drying the prepared solution B to obtain an adsorption material for repairing arsenic and antimony contaminated surface water.

[0028] The present application provides a method for preparing an adsorption material for repairing surface water bodies contaminated by arsenic and antimony. The active zinc oxide particles are first etched with alkali to obtain more active sites, while releasing zinc ions. This can effectively promote the transfer and diffusion of ions during the material preparation process, and utilize the released zinc ions and the added lanthanum and iron elements to co-precipitate in the pores to form a special double-layer metal hydroxide of zinc, iron and lanthanum, forming a core-shell structure with a special metal-hydroxyl group and an inner sphere complexation effect, thereby improving the adsorption selectivity for arsenic and antimony. At the same time, the double-layer metal hydroxide is loaded with amino groups between the layers, further increasing the selectivity for arsenic and antimony. Compared with other adsorbents on the market, it has a different separation principle. The present application mainly relies on the selective adsorption of the zinc, iron and lanthanum double-layer metal hydroxide and the amino group for the adsorption treatment of heavy metals.

[0029] In some embodiments, the particle size of the active zinc oxide particles in step S100 is 1 mm to 3 mm, for example, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, or any value between 1 and 3 mm.

[0030] In some embodiments, the concentration of the first sodium hydroxide solution in step S100 is 1 mol / L to 3 mol / L, for example, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, or any value between 1 mol / L and 3 mol / L.

[0031] In some embodiments, the mass volume ratio of the active zinc oxide particles to the first sodium hydroxide solution in step S100 is 1 g: (10-20) mL, for example, it can be 1 g: 10 mL, 1 g: 15 mL, 1 g: 20 mL or any ratio between 1 g: (10-20) mL.

[0032] In some embodiments, the mass percentage concentration of the proline solution in step S200 is 6% to 10%, for example, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt% or any value between 6 wt% and 10 wt%.

[0033] In some embodiments, the mass volume ratio of the modified active zinc oxide particles to the proline solution in step S200 is 1 g: (10-20) mL, for example, 1 g: 10 mL, 1 g: 15 mL, 1 g: 20 mL, or any ratio between 1 g: (10-20) mL.

[0034] In some embodiments, the concentration of the second sodium hydroxide solution in step S200 is 1 mol / L to 3 mol / L, for example, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, or any value between 1 mol / L and 3 mol / L.

[0035] In some embodiments, the mass volume ratio of the modified active zinc oxide particles to the second sodium hydroxide solution in step S200 is 1 g: (5-20) mL, for example, 1 g: 5 mL, 1 g: 6 mL, 1 g: 7 mL, 1 g: 8 mL, 1 g: 9 mL, 1 g: 10 mL, 1 g: 13 mL, 1 g: 15 mL, 1 g: 17 mL, 1 g: 20 mL or any ratio between 1 g: (5-20) mL.

[0036] In some embodiments, the mass ratio of the iron salt, the modified active zinc oxide particles, and the lanthanum salt is (2-3):1:0.1, for example, it can be any value between 2:1:0.1, 3:1:0.1, or (2-3):1:0.1.

[0037] In some embodiments, the iron salt is ferric chloride and / or ferric sulfate, and the lanthanum salt is lanthanum chloride and / or lanthanum nitrate.

[0038] In some embodiments, the time for the first stirring in step S200, the second stirring in step S300, and the mixing stirring in step S100 are independently 1 h to 2 h, for example, 1 h, 2 h, or any value between 1 h and 2 h.

[0039] In some embodiments, the standing time in step S300 is 2 hours to 5 hours, for example, it can be 2 hours, 3 hours, 4 hours, 5 hours, or any value between 2 hours and 5 hours.

[0040] In some embodiments, the pH of both Preparation Solution A and Preparation Solution B is 10.5 or above, for example, 10.5, 11, 12, or any value of 10.5 or above. The pH of the washed material is neutral.

[0041] In some embodiments, the vacuum drying temperature is 80°C~100°C, for example, it can be 80°C, 90°C, 100°C or any value between 80°C~100°C, and the time is 10h~12h, for example, it can be 10h, 11h, 12h or any value between 10h~12h.

[0042] The present application also provides an adsorption material for repairing surface water bodies contaminated by arsenic and antimony, which is prepared by the above-mentioned method for preparing the adsorption material for repairing surface water bodies contaminated by arsenic and antimony.

[0043] In some embodiments, the adsorption material has a particle size of 1 mm to 3 mm, accounting for greater than or equal to 98 wt %.

[0044] The adsorption material provided in this application for repairing arsenic and antimony contaminated surface water has a large particle size, is not easy to clog, has good selectivity, has a large adsorption capacity, is good in stability, and does not require frequent regeneration.

[0045] The present application also provides a method for treating arsenic- and antimony-containing wastewater, which uses the above-mentioned adsorption material for repairing arsenic- and antimony-contaminated surface water to treat the arsenic- and antimony-containing wastewater.

[0046] In some embodiments, the adsorption material for repairing arsenic- and antimony-contaminated surface water is mixed with the arsenic- and antimony-containing wastewater; and the treatment is performed at a pH of 6-10.

[0047] The mass volume ratio of the adsorption material to the mercury- and thallium-containing wastewater is 1 g: (500-2000) mL, for example, it can be 1 g: 500 mL, 1 g: 600 mL, 1 g: 700 mL, 1 g: 800 mL, 1 g: 900 mL, 1 g: 1000 mL, 1 g: 1200 mL, 1 g: 1500 mL, 1 g: 1700 mL, 1 g: 2000 mL or any ratio between 1 g: (500-2000) mL; the pH can be, for example, 6, 7, 8, 9, 10 or any value between 6 and 10.

[0048] The adsorption material for repairing arsenic and antimony contaminated surface water provided in this application is used to treat arsenic and antimony-containing wastewater. The surface water can meet the surface water environmental quality standards after treatment with high efficiency and low cost.

[0049] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, the conditions are carried out according to conventional conditions or manufacturer recommendations. The reagents or instruments used are not specified by the manufacturer and are conventional products that can be purchased commercially.

[0050] Example 1 This embodiment provides an adsorption material for repairing arsenic and antimony contaminated surface water, and the preparation method thereof is as follows: 1) 5g of active zinc oxide particles with a particle size of 1~3mm (Scanning electron microscope photo as shown Figure 2 50 mL of sodium hydroxide solution (1 mol / L) was added to the left part of the mixture, stirred for 2 h, and filtered to form modified active zinc oxide particles.

[0051] 2) Add lanthanum salt, proline solution (6 wt.%), and sodium hydroxide solution (2 mol / L) to the modified active zinc oxide particles in a ratio of 1 g:0.1 g:10 mL:10 mL and stir for 1 h to form preparation solution A.

[0052] 3) Add iron salt to Preparation Solution A in a ratio of 2g:1g iron salt to activated zinc oxide particles. Stir for 1 hour and let stand for 2 hours to form Preparation Solution B.

[0053] 4) Solution B was filtered, washed repeatedly with deionized water and ethanol for 60 minutes, and then dried in a vacuum drying oven at 80° C. for 10 hours to obtain the adsorption material for repairing arsenic and antimony contaminated surface water of Example 1.

[0054] The obtained SEM photograph of the adsorption material used to repair arsenic and antimony contaminated surface water is shown in the figure. Figure 2 As shown in the right part, the infrared spectrum is as follows Figure 3 As shown, the material is 3334.3cm -1 There are obvious hydroxyl stretching vibration peaks and amine stretching vibration peaks. In addition, at 1622.68cm -1 The amine bending vibration peaks appear at 1550.28 cm -1 、1408.15 cm -1 、1039.77 cm -1 Metal-hydroxyl vibration peaks appeared.

[0055] Arsenic- and antimony-contaminated wastewater was treated using the above-mentioned adsorption material for remediation of arsenic- and antimony-contaminated surface water bodies. The mass-to-volume ratio was 1 g:1000 mL, and the system pH was 7. The treatment results are shown in Table 1 below.

[0056] Table 1 Experimental data of the adsorption material of Example 1 for treating wastewater containing arsenic and antimony

[0057] As can be seen from Table 1, the adsorption material used in Example 1 to repair arsenic and antimony contaminated surface water treats heavy metal wastewater, and the heavy metal content after treatment can reach the surface water Class III standard or the centralized drinking water surface water source standard.

[0058] Example 2 This embodiment provides an adsorption material for repairing arsenic and antimony contaminated surface water, and the preparation method thereof is as follows: 1) Add 75 mL of sodium hydroxide solution (2 mol / L) to 5 g of activated zinc oxide particles with a particle size of 1-3 mm, stir for 2 h, and filter to form modified activated zinc oxide particles.

[0059] 2) Add lanthanum salt, proline solution (8 wt.%), and sodium hydroxide solution (2 mol / L) to the modified active zinc oxide particles in a ratio of 1 g:0.1 g:15 mL:5 mL, and stir for 1 h to form preparation solution A.

[0060] 3) Add iron salt to Preparation Solution A at a ratio of 2 g:1 g of iron salt and modified activated zinc oxide particles, stir for 1 hour, and let stand for 4 hours to form Preparation Solution B.

[0061] 4) Solution B was filtered, washed repeatedly with deionized water and ethanol for 60 minutes, and then dried in a vacuum drying oven at 80° C. for 12 hours to obtain the adsorption material for remediation of arsenic and antimony contaminated surface water of Example 2.

[0062] Arsenic- and antimony-contaminated wastewater was treated using the above-mentioned adsorption material for remediation of arsenic- and antimony-contaminated surface water bodies. The mass-to-volume ratio was 1 g:800 mL, and the system pH was 9. The treatment results are shown in Table 2 below.

[0063] Table 2 Experimental data of the adsorption material of Example 2 for treating wastewater containing arsenic and antimony

[0064] As can be seen from Table 2, the adsorption material used in Example 2 for repairing arsenic and antimony contaminated surface water treats heavy metal contaminated surface water, and the heavy metal content after treatment can reach the surface water Class III standard or the centralized drinking water surface water source standard.

[0065] Example 3 This embodiment provides an adsorption material for repairing arsenic and antimony contaminated surface water, and the preparation method thereof is as follows: 1) Add 75 mL of sodium hydroxide solution (3 mol / L) to 5 g of active zinc oxide particles with a particle size of 1-3 mm, stir for 2 h, and filter to form modified active zinc oxide particles.

[0066] 2) Add lanthanum salt, proline solution (10 wt.%), and sodium hydroxide solution (3 mol / L) to the modified active zinc oxide particles in a ratio of 1 g:0.1 g:20 mL:20 mL and stir for 1 h to form preparation solution A.

[0067] 3) Add iron salt to Preparation Solution A in a ratio of 3 g:1 g of iron salt and modified activated zinc oxide particles, stir for 1 hour, and let stand for 4 hours to form Preparation Solution B.

[0068] 4) Solution B was filtered, washed repeatedly with deionized water and ethanol for 60 minutes, and then dried in a vacuum drying oven at 80° C. for 12 hours to obtain the adsorption material for remediation of arsenic and antimony contaminated surface water of Example 3.

[0069] Arsenic- and antimony-contaminated wastewater was treated using the above-mentioned adsorption material for remediation of arsenic- and antimony-contaminated surface water bodies. The mass-to-volume ratio was 1 g:1200 mL, and the system pH was 10. The treatment results are shown in Table 3 below.

[0070] Table 3 Experimental data of the adsorption material of Example 3 for treating wastewater containing arsenic and antimony

[0071] As can be seen from Table 3, the adsorption material used in Example 3 to repair arsenic and antimony contaminated surface water treats heavy metal contaminated surface water, and the heavy metal content after treatment can reach the surface water Class III standard or the centralized drinking water surface water source standard.

[0072] Comparative Example 1 This comparative example provides an adsorption material for repairing arsenic and antimony contaminated surface water. Compared with Example 1, the adsorption material is not modified with alkali. The preparation method is as follows: 1) Add lanthanum salt, proline solution (6 wt.%), and sodium hydroxide solution (2 mol / L) to the activated zinc oxide particles in a ratio of 1 g:0.1 g:10 mL:10 mL. Stir for 1 h to form preparation solution A.

[0073] 2) Add iron salt to Preparation Solution A in a ratio of 2g:1g of iron salt and activated zinc oxide particles. Stir for 1 hour and let stand for 2 hours to form Preparation Solution B.

[0074] 3) Filtering the prepared solution B, repeatedly washing with deionized water and ethanol for 60 minutes, and then drying it in a vacuum drying oven at 80° C. for 10 hours to prepare an adsorption material for repairing arsenic and antimony contaminated surface water.

[0075] Arsenic- and antimony-contaminated wastewater was treated using the above-mentioned adsorption material for remediation of arsenic- and antimony-contaminated surface water bodies. The mass-to-volume ratio was 1 g:1000 mL, and the system pH was 7. The treatment results are shown in Table 4 below.

[0076] Table 4 Experimental data of the adsorption material of Comparative Example 1 for treating wastewater containing arsenic and antimony

[0077] As can be seen from Table 4, the adsorption material used in Comparative Example 1 to repair arsenic and antimony contaminated surface water to treat heavy metal contaminated surface water cannot meet the Class III surface water standard or the centralized drinking water surface water source standard.

[0078] This is because base modification of the active zinc oxide particles releases more active sites and generates free zinc ions around the particles. More active sites can bind to more amine groups, and the free zinc ions can form a double-layer metal hydroxide with lanthanum at the active sites. The subsequent addition of iron can replace some of the lanthanum to form a special zinc-iron-lanthanum double-layer metal hydroxide. These amino functional groups and the special double-layer metal hydroxide together lead to the material's high adsorption capacity and selectivity.

[0079] Comparative Example 2 This comparative example provides an adsorption material for repairing arsenic and antimony contaminated surface water. Compared with Example 3, no lanthanum salt is added in step 2. The preparation method is as follows: 1) Add 75 mL of sodium hydroxide solution (3 mol / L) to 5 g of active zinc oxide particles with a particle size of 1-3 mm, stir for 2 h, and filter to form modified active zinc oxide particles.

[0080] 2) Add proline solution (10 wt.%) and sodium hydroxide solution (3 mol / L) to the modified active zinc oxide particles in a ratio of 1 g:20 mL:20 mL and stir for 1 h to form preparation solution A.

[0081] 3) Add iron salt to Preparation Solution A in a ratio of 3 g:1 g of iron salt and modified activated zinc oxide particles, stir for 1 hour, and let stand for 4 hours to form Preparation Solution B.

[0082] 4) Filtering the prepared solution B, repeatedly washing with deionized water and ethanol for 60 minutes, and then drying in a vacuum drying oven at 80° C. for 12 hours to prepare an adsorption material for remediation of arsenic and antimony contaminated surface water.

[0083] Arsenic- and antimony-contaminated wastewater was treated using the above-mentioned adsorption material for remediation of arsenic- and antimony-contaminated surface water bodies. The mass-to-volume ratio was 1 g:1200 mL, and the system pH was 10. The treatment results are shown in Table 5 below.

[0084] Table 5 Experimental data of the adsorption material of Comparative Example 2 for treating wastewater containing arsenic and antimony

[0085] As can be seen from Table 5, the adsorption material used in Comparative Example 2 to repair arsenic and antimony contaminated surface water to treat heavy metal contaminated surface water cannot meet the Class III surface water standard or the centralized drinking water surface water source standard.

[0086] This is because lanthanum is not added to the modified active zinc oxide particles, and the free zinc ions form zinc hydroxide, not a special double-layer metal hydroxide. Iron cannot be replaced subsequently, and a double-layer metal hydroxide with high adsorption capacity and selectivity cannot be obtained.

[0087] Comparative Example 3 This comparative example provides an adsorption material for repairing arsenic and antimony contaminated surface water. Compared with Example 3, no iron salt is added. The preparation method thereof is as follows: 1) Add 75 mL of sodium hydroxide solution (3 mol / L) to 5 g of active zinc oxide particles with a particle size of 1-3 mm, stir for 2 h, and filter to form modified active zinc oxide particles.

[0088] 2) Add lanthanum salt, proline solution (10 wt.%), and sodium hydroxide solution (3 mol / L) to the modified active zinc oxide particles in a ratio of 1 g:0.1 g:20 mL:20 mL, and stir for 1 h to form a prepared solution.

[0089] 3) The prepared solution was filtered, repeatedly washed with deionized water and ethanol for 60 minutes, and then dried in a vacuum drying oven at 80° C. for 12 hours to prepare the adsorption material for repairing arsenic and antimony contaminated surface water of Comparative Example 3.

[0090] Arsenic- and antimony-contaminated wastewater was treated using the above-mentioned adsorption material for remediation of arsenic- and antimony-contaminated surface water bodies. The mass-to-volume ratio was 1 g:1200 mL, and the system pH was 10. The treatment results are shown in Table 6 below.

[0091] Table 6 Experimental data of the adsorption material of Comparative Example 3 for treating wastewater containing arsenic and antimony

[0092] As shown in Table 6, the adsorption material used in Comparative Example 3 for remediating arsenic- and antimony-contaminated surface water treated heavy metal-contaminated surface water failed to meet the Class III surface water standard or the standard for centralized drinking water sources. This is because iron is selective for arsenic and antimony, and its absence would have resulted in a less effective treatment.

[0093] Comparative Example 4 This comparative example provides an adsorption material for repairing arsenic and antimony contaminated surface water. Compared with Example 3, no proline solution is added. The preparation method thereof is as follows: 1) Add 75 mL of sodium hydroxide solution (3 mol / L) to 5 g of active zinc oxide particles with a particle size of 1-3 mm, stir for 2 h, and filter to form modified active zinc oxide particles.

[0094] 2) Add lanthanum salt and sodium hydroxide solution (3 mol / L) to the modified active zinc oxide particles in a ratio of 1 g:0.1 g:20 mL and stir for 1 h to form preparation solution A.

[0095] 3) Add iron salt to Preparation Solution A in a ratio of 3 g:1 g of iron salt and modified activated zinc oxide particles, stir for 1 hour, and let stand for 4 hours to form Preparation Solution B.

[0096] 4) Solution B was filtered and repeatedly washed with deionized water and ethanol for 60 minutes, and then dried in a vacuum drying oven at 80° C. for 12 hours to obtain the adsorption material for repairing arsenic and antimony contaminated surface water of Comparative Example 4.

[0097] Arsenic- and antimony-contaminated wastewater was treated using the above-mentioned adsorption material for remediation of arsenic- and antimony-contaminated surface water bodies. The mass-to-volume ratio was 1 g:1200 mL, and the system pH was 10. The treatment results are shown in Table 7 below.

[0098] Table 7 Experimental data of the adsorption material of Comparative Example 4 for treating wastewater containing arsenic and antimony

[0099] As can be seen from Table 7, the adsorption material used in Comparative Example 4 to repair arsenic and antimony contaminated surface water to treat heavy metal contaminated surface water cannot meet the Class III surface water standard or the centralized drinking water surface water source standard after treatment.

[0100] This is because the amino groups in the proline solution are selective groups for adsorbing arsenic and antimony and can combine with arsenic and antimony.

[0101] Comparative Example 5 This comparative example provides an adsorption material for repairing arsenic and antimony contaminated surface water. Compared with Example 3, no sodium hydroxide solution is added in step 2. The preparation method is as follows: 1) Add 75 mL of sodium hydroxide solution (3 mol / L) to 5 g of active zinc oxide particles with a particle size of 1-3 mm, stir for 2 h, and filter to form modified active zinc oxide particles.

[0102] 2) Add lanthanum salt and proline solution (10 wt.%) to the modified active zinc oxide particles in a ratio of 1 g:0.1 g:20 mL and stir for 1 h to form preparation solution A.

[0103] 3) Add iron salt to Preparation Solution A in a ratio of 3 g:1 g of iron salt and modified activated zinc oxide particles, stir for 1 hour, and let stand for 4 hours to form Preparation Solution B.

[0104] 4) Solution B was filtered and repeatedly washed with deionized water and ethanol for 60 minutes, and then dried in a vacuum drying oven at 80° C. for 12 hours to obtain the adsorption material for repairing arsenic and antimony contaminated surface water of Comparative Example 5.

[0105] Arsenic- and antimony-contaminated wastewater was treated using the above-mentioned adsorption material for remediation of arsenic- and antimony-contaminated surface water bodies. The mass-to-volume ratio was 1 g:1200 mL, and the system pH was 10. The treatment results are shown in Table 8 below.

[0106] Table 8 Experimental data of the adsorption material of Comparative Example 5 for treating wastewater containing arsenic and antimony

[0107] As can be seen from Table 8, the adsorption material used in Comparative Example 5 to repair arsenic and antimony contaminated surface water to treat heavy metal contaminated surface water cannot meet the Class III surface water standard or the centralized drinking water surface water source standard after treatment.

[0108] This is because without the addition of sodium hydroxide, a double-layer metal hydroxide cannot be formed, and functional groups cannot be formed on the zinc oxide particles, resulting in poor adsorption performance.

[0109] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

[0110] Furthermore, those skilled in the art will appreciate that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and to form distinct embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is intended solely to enhance understanding of the overall background of this application and should not be construed as an admission or any implication that such information constitutes prior art known to those skilled in the art.

Claims

1. A method for preparing an adsorption material for repairing arsenic and antimony contaminated surface water, characterized in that: include: Mixing and stirring the active zinc oxide particles and the first sodium hydroxide solution to obtain modified active zinc oxide particles; Adding the lanthanum salt, the proline solution and the second sodium hydroxide solution to the modified active zinc oxide particles respectively, and performing a first stirring to form a preparation solution A; Adding iron salt to the prepared solution A, performing a second stirring and allowing to stand to form a prepared solution B; The prepared solution B is filtered, washed, and vacuum-dried to obtain the adsorption material for repairing arsenic- and antimony-contaminated surface water.

2. The method for preparing an adsorption material for repairing arsenic and antimony contaminated surface water according to claim 1, characterized in that: The particle size of the active zinc oxide particles is 1 mm to 3 mm, the concentration of the first sodium hydroxide solution is 1 mol / L to 3 mol / L; the mass volume ratio of the active zinc oxide particles to the first sodium hydroxide solution is 1 g: (10-20) mL.

3. The method for preparing an adsorption material for repairing arsenic and antimony contaminated surface water according to claim 1, characterized in that: The mass percentage concentration of the proline solution is 6% to 10%, and the mass volume ratio of the modified active zinc oxide particles to the proline solution is 1 g: (10 to 20) mL; And / or, the concentration of the second sodium hydroxide solution is 1 mol / L to 3 mol / L; the mass volume ratio of the modified active zinc oxide particles to the second sodium hydroxide solution is 1 g: (5 to 20) mL.

4. The method for preparing an adsorption material for repairing arsenic and antimony contaminated surface water according to claim 1, characterized in that: The mass ratio of the iron salt, the modified active zinc oxide particles, and the lanthanum salt is (2-3):1:0.

1.

5. The method for preparing an adsorption material for repairing arsenic and antimony contaminated surface water according to claim 1, characterized in that: The iron salt is ferric chloride and / or ferric sulfate, and the lanthanum salt is lanthanum chloride and / or lanthanum nitrate.

6. The method for preparing an adsorption material for repairing arsenic and antimony contaminated surface water according to any one of claims 1 to 5, characterized in that: At least one of the following conditions is met: A. The time for the first stirring, the second stirring, and the mixed stirring is independently 1 hour to 2 hours; B. The standing time is 2h~5h; C. The pH of the prepared solution A and the prepared solution B are both 10.5 and above; D. the pH of the washed material is neutral; E. The vacuum drying temperature is 80°C to 100°C, and the time is 10h to 12h.

7. An adsorption material for repairing arsenic and antimony contaminated surface water, characterized in that: The adsorption material is prepared by the preparation method of any one of claims 1 to 6 for repairing arsenic and antimony contaminated surface water.

8. The adsorption material for repairing arsenic and antimony contaminated surface water according to claim 7, characterized in that: The adsorption material has a particle size of 1 mm to 3 mm, and the proportion of the adsorption material is greater than or equal to 98 wt %.

9. A method for treating wastewater containing arsenic and antimony, characterized in that: The adsorption material for repairing arsenic- and antimony-contaminated surface water bodies according to claim 7 or 8 is used to treat arsenic- and antimony-containing wastewater.

10. The method for treating wastewater containing arsenic and antimony according to claim 9, characterized in that: The adsorption material for repairing arsenic- and antimony-contaminated surface water is mixed with the arsenic- and antimony-containing wastewater; and the treatment is performed under a pH value of 6-10.

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