Acidic antimony ore wastewater heavy metal adsorbent as well as preparation method and application thereof

Abstract

The invention discloses a preparation method of an acidic antimony ore wastewater heavy metal adsorbent. The preparation method comprises the following steps: S1, preparing a pasty uniform sodium alginate aqueous solution; s2, adding electrolytic manganese residues to form a first solution; s3, adding an APS initiator solution to obtain a second solution; s4, adding a sodium hydroxide solution and an AA solution to obtain a third solution; s5, adding an AM solution to obtain a fourth solution; s6, adding an MBA solution to obtain a fifth solution; and carrying out a cross-linking reaction under water culture, washing with water until the product is neutral, and drying. The invention further provides the heavy metal adsorbent for the acidic antimony ore wastewater. The heavy metal adsorbent is prepared by adopting the preparation method. The invention further provides application of the heavy metal adsorbent for the acidic antimony ore wastewater. The heavy metal adsorbent is applied to removal of lead and antimony heavy metals in the acidic antimony ore wastewater. The invention not only provides a new material for adsorbing lead and antimony heavy metals in the acidic antimony ore wastewater, but also provides a new way for high-value recycling of the electrolytic manganese residues.

Description

Technical Field

[0001] The invention belongs to the technical field of environmental heavy metal removal, and particularly relates to a heavy metal adsorbent for acidic antimony mine wastewater, a preparation method and an application thereof. Background Art

[0002] Acidic antimony mine wastewater is a typical type of mining wastewater. Typical heavy metal ions in antimony mine wastewater include lead, antimony, and other heavy metals. These metals, when introduced into plants, animals, and humans, accumulate in the body, causing death and the risk of malformation and cancer in humans. Due to its low pH and high heavy metal content, acidic antimony mine wastewater treatment typically utilizes a combination of electrochemical and coagulation methods. However, these methods are energy-intensive and prohibitive for small and medium-sized antimony mines. Consequently, most small and medium-sized antimony mines utilize adsorption methods for wastewater treatment. However, these methods face challenges such as high adsorbent consumption, high costs, and pH sensitivity.

[0003] The acid leaching residue produced by electrolytic manganese metal is called electrolytic manganese residue (EMR). Every ton of manganese metal produced will produce 7-9 tons of electrolytic manganese residue. EMR is a Class II general industrial solid waste, and the accumulation of large amounts of manganese residue will cause a waste of land resources. From the chemical composition of electrolytic manganese residue, electrolytic manganese residue is mainly composed of silicon dioxide, aluminum oxide, iron oxide, magnesium oxide, etc. Therefore, the resource utilization of electrolytic manganese residue is of great practical significance. Summary of the Invention

[0004] The purpose of the present invention is to provide a heavy metal adsorbent for acidic antimony mine wastewater, a preparation method and application thereof, so as to solve the problem raised in the background technology that most small and medium-sized antimony mine wastewater treatment currently adopts adsorption method, but faces the problems of large adsorbent consumption, high cost, and pH sensitivity, as well as the problem that the accumulation of a large amount of manganese slag will cause waste of land resources and require harmless resource treatment.

[0005] To achieve the above object, the present invention provides a method for preparing a heavy metal adsorbent for acidic antimony mine wastewater, comprising the following steps: S1, adding sodium alginate to an aqueous solution, stirring at a constant temperature to obtain a paste-like uniform sodium alginate aqueous solution; S2, adding electrolytic manganese slag to the sodium alginate aqueous solution, stirring and ultrasonicating to form a uniform first solution; S3, preparing an ammonium persulfate (APS) initiator solution, adding it to the first solution to obtain a second solution; S4, preparing a sodium hydroxide solution and an acrylic acid (AA) solution, and adding them to the second solution to obtain a third solution; S5. Prepare an acrylamide (AM) solution and add it to the third solution to obtain a fourth solution; S6. Prepare NN methylenebisacrylamide (MBA) solution and add it to the fourth solution to obtain a fifth solution; The fifth solution was subjected to a cross-linking reaction under hydroponic conditions at 60-65° C. After the cross-linking reaction, the adsorption gel was washed with deionized water until neutral and dried to obtain a sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent.

[0006] In a specific embodiment, in step S6, the cross-linking reaction time is 8 to 12 hours.

[0007] In a specific embodiment, in step S1, the sodium alginate is analytical grade; the mass-to-liquid ratio of the sodium alginate aqueous solution is 5g:35-45ml; the stirring temperature is 80-90°C, and the stirring time is 30-40min.

[0008] In a specific embodiment, in step S2, the stirring ultrasonic treatment includes stirring at a rotation speed of 30 r / min for 15 to 20 minutes, and ultrasonicating at an ultrasonic power of 200 W for 15 to 30 minutes; the pretreatment of the electrolytic manganese slag includes: calcining at 400-600° C., crushing, and then passing through a 100 mesh sieve to obtain the undersize.

[0009] In a specific embodiment, the mass ratio of sodium alginate to electrolytic manganese slag is 5:2-3; the mass ratio of sodium alginate to ammonium persulfate (APS) initiator is 5:0.1-0.15; the mass ratio of sodium alginate to sodium hydroxide is 5:1-1.5; the mass volume ratio of sodium alginate to acrylic acid (AA) is 5g:3-5ml; the mass ratio of sodium alginate to acrylamide (AM) is 5:0.8-1.2; and the mass ratio of sodium alginate to NN methylenebispropylene (MBA) is 5:0.3-0.4.

[0010] In a specific embodiment, in step S3, the temperature when the first solution is added is 75~80°C, and the reaction is carried out for 3~5 minutes after the first solution is added; in step S4, the temperature when the second solution is added is 75~80°C, and the reaction is carried out for 3~5 minutes after the second solution is added; in step S5, the temperature when the third solution is added is 75~80°C, and the reaction is carried out for 3~5 minutes after the third solution is added.

[0011] In a specific embodiment, in step S6, the drying temperature is 60-80°C.

[0012] The present invention also provides a heavy metal adsorbent for acidic antimony mine wastewater, which is prepared by the above-mentioned preparation method of the heavy metal adsorbent for acidic antimony mine wastewater.

[0013] The present invention also provides an application of a heavy metal adsorbent for acidic antimony mine wastewater. The heavy metal adsorbent for acidic antimony mine wastewater is the heavy metal adsorbent for acidic antimony mine wastewater as described above, and is applied to remove heavy metals such as lead and antimony from acidic antimony mine wastewater.

[0014] In a specific embodiment, the pH of the acidic antimony mine wastewater is first adjusted to 4-6, and the amount of the heavy metal adsorbent for acidic antimony mine wastewater added to each liter of acidic antimony mine wastewater is 0.6-1 g.

[0015] Compared with the prior art, the present invention has the following beneficial effects: This invention uses Class II general industrial solid waste, electrolytic manganese slag, as raw material, mixed with composite sodium alginate and polyacrylamide to prepare a highly efficient selective adsorption gel via a simple hydrothermal method. This provides a new material for adsorbing heavy metals such as lead and antimony from acidic antimony mine wastewater and offers a new path for high-value resource recovery from electrolytic manganese slag.

[0016] The chemical composition of electrolytic manganese slag shows that it is primarily composed of silicon dioxide, aluminum oxide, iron oxide, and magnesium oxide, with clay-like mineral properties. Using electrolytic manganese slag alone as a heavy metal adsorbent has drawbacks such as difficulty in particle recovery and low adsorption capacity.

[0017] The highly efficient selective adsorption gel prepared by the present invention overcomes the difficulties of separating and recycling conventional activated electrolytic manganese slag adsorbent powders, as well as the poor mechanical properties of sodium alginate-based adsorbents. Furthermore, the present invention exhibits excellent adsorption properties for single lead and antimony heavy metal ions, and when both heavy metals are present, the composite adsorbent exhibits excellent selective adsorption for trivalent antimony ions. Therefore, the present invention not only provides a new path for the high-value resource recovery of electrolytic manganese slag, but also provides a novel material for the adsorption and removal of lead, antimony and heavy metal ions from acidic antimony mine wastewater.

[0018] In addition to the above-described objects, features and advantages, the present invention has other objects, features and advantages. The present invention is further described in detail below. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings: Figure 1 The present invention is a flow chart of a method for preparing a heavy metal adsorbent for acidic antimony mine wastewater.

[0020] Figure 2 It is the TG thermogravimetric diagram of the sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent prepared by the present invention; Figure 2It can be seen that the sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent prepared by the present invention has a heat loss of 41% within 600° C., which is mainly due to the loss of mass of the natural polysaccharide sodium alginate and the polyacrylamide formed by polymerization.

[0021] Figure 3 This is the SEM image of the sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent prepared by the present invention. Figure 3 It can be seen that the sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent has a porous structure.

[0022] Figure 4 This is the FTIR graph of the sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent prepared by the present invention. Figure 4 It can be seen that the sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent prepared by the present invention has abundant oxygen-containing functional groups, amide groups and silicon-oxygen bonds, which provide a functional group basis for the subsequent adsorption and complexation of lead and antimony heavy metals, indicating that the adsorbent was successfully prepared. DETAILED DESCRIPTION

[0023] The embodiments of the present invention are described in detail below. The specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0024] The present invention provides a method for preparing a heavy metal adsorbent for acidic antimony mine wastewater, comprising the following steps: S1, adding sodium alginate to an aqueous solution, stirring at a constant temperature to obtain a paste-like uniform sodium alginate aqueous solution; S2, adding electrolytic manganese slag to the sodium alginate aqueous solution, stirring and ultrasonicating to form a uniform first solution; S3, preparing an ammonium persulfate (APS) initiator solution, adding it to the first solution to obtain a second solution; S4, preparing a sodium hydroxide solution and an acrylic acid (AA) solution, and adding them to the second solution to obtain a third solution; S5. Prepare an acrylamide (AM) solution and add it to the third solution to obtain a fourth solution; S6. Prepare NN methylenebisacrylamide (MBA) solution and add it to the fourth solution to obtain a fifth solution; The fifth solution was subjected to a cross-linking reaction under hydroponic conditions at 60-65° C. After the cross-linking reaction, the adsorption gel was washed with deionized water until neutral and dried to obtain a sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent.

[0025] When the hydroponic culture temperature is below 60℃, it cannot be formed within the appropriate time and it takes a longer time to form an adsorption gel; when the hydroponic culture temperature is above 65℃, cross-linking is often unsuccessful, and it becomes a hard lump without elasticity.

[0026] In step S6, the cross-linking reaction time is 8 to 12 hours.

[0027] In step S1, the sodium alginate is analytical grade; the mass-to-liquid ratio of the sodium alginate aqueous solution is 5 g:35-45 ml; the stirring temperature is 80-90° C., and the stirring time is 30-40 min.

[0028] In step S2, the stirring ultrasonic treatment includes stirring at a rotation speed of 30 r / min for 15 to 20 minutes, and ultrasonicating at an ultrasonic power of 200 W for 15 to 30 minutes; the pretreatment of the electrolytic manganese slag includes: calcining at 400-600° C., crushing, and then passing through a 100-mesh sieve to obtain a sieve undersize.

[0029] The mass ratio of sodium alginate to electrolytic manganese slag is 5:2-3; the mass ratio of sodium alginate to ammonium persulfate (APS) initiator is 5:0.1-0.15; the mass ratio of sodium alginate to sodium hydroxide is 5:1-1.5; the mass volume ratio of sodium alginate to acrylic acid (AA) is 5g:3-5ml; the mass ratio of sodium alginate to acrylamide (AM) is 5:0.8-1.2; and the mass ratio of sodium alginate to NN methylenebispropylene (MBA) is 5:0.3-0.4.

[0030] In step S3, the temperature when the first solution is added is 75-80°C, and the reaction takes 3-5 minutes after the first solution is added; in step S4, the temperature when the second solution is added is 75-80°C, and the reaction takes 3-5 minutes after the second solution is added; in step S5, the temperature when the third solution is added is 75-80°C, and the reaction takes 3-5 minutes after the third solution is added.

[0031] In step S6, the drying temperature is 60-80°C.

[0032] The present invention also provides a heavy metal adsorbent for acidic antimony mine wastewater, which is prepared by the above-mentioned preparation method of the heavy metal adsorbent for acidic antimony mine wastewater.

[0033] The present invention also provides an application of a heavy metal adsorbent for acidic antimony mine wastewater. The heavy metal adsorbent for acidic antimony mine wastewater is the heavy metal adsorbent for acidic antimony mine wastewater as described above, and is applied to remove heavy metals such as lead and antimony from acidic antimony mine wastewater.

[0034] First, the pH of the acidic antimony mine wastewater is adjusted to 4-6, and the amount of the acidic antimony mine wastewater heavy metal adsorbent added to each liter of the acidic antimony mine wastewater is 0.6-1g.

[0035] Example 1 A method for preparing a heavy metal adsorbent for acidic antimony mine wastewater comprises the following steps: S1. Accurately weigh 5 g of sodium alginate into a beaker, add 40 ml of deionized water, place on a magnetic stirrer at 90°C, 30 rpm and stir for 30 min to obtain a uniform paste of sodium alginate aqueous solution.

[0036] S2. Accurately weigh 2 g of electrolytic manganese slag and add it to the uniformly gelatinized sodium alginate solution in step 1. Stir at 30 rpm for 15 min. Place the mixture in an ultrasonic cleaner with an ultrasonic power of 200 W for 15 min to obtain a uniformly mixed sodium alginate / electrolytic manganese slag solution.

[0037] S3. Accurately weigh 0.1 g of ammonium persulfate (APS) initiator, dissolve it in 2 ml of deionized water, add the sodium alginate / electrolytic manganese slag solution in step 2 at 75°C, and react for 3 minutes.

[0038] S4. Accurately weigh 1g of sodium hydroxide and dissolve it in 10ml of deionized water. Measure 4ml of acrylic acid (AA) and add it to the solution in step 3 at 75°C and react for 5min.

[0039] S5. Accurately weigh 1 g of acrylamide (AM), dissolve it in 5 ml of deionized water, add it to the solution in step 4 at 75°C, and react for 5 minutes.

[0040] S6. Accurately weigh 0.4 g of N-N-methylenebispropylene (MBA), dissolve it in 20 ml of deionized water, add it to the solution in step 5, culture it in water at 65 ° C, and cross-link it for 8 hours. After the reaction is completed, rinse it with deionized water until it is neutral, and dry it at 60 ° C to obtain sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent, which is recorded as SA-EMR. 5∶2 .

[0041] Example 2 A method for preparing a heavy metal adsorbent for acidic antimony mine wastewater comprises the following steps: S1. Accurately weigh 5g of sodium alginate into a beaker, add 40ml of deionized water, place on a magnetic stirrer at 90℃, 30r / min and stir for 30min.

[0042] S2. Accurately weigh 2.5 g of electrolytic manganese slag and add it to the uniformly gelatinized sodium alginate solution in step 1. Stir at 30 rpm for 15 min. Place the mixture in an ultrasonic cleaner with an ultrasonic power of 200 W and ultrasonicate for 15 min to obtain a uniformly mixed sodium alginate / electrolytic manganese slag solution.

[0043] S3. Accurately weigh 0.1 g of ammonium persulfate (APS) initiator, dissolve it in 2 ml of deionized water, add the sodium alginate / electrolytic manganese slag solution in step 2 at 75°C, and react for 3 minutes.

[0044] S4. Accurately weigh 1g of sodium hydroxide and dissolve it in 10ml of deionized water. Measure 4ml of acrylic acid (AA) and add it to the solution in step 3 at 75°C and react for 5min.

[0045] S5. Accurately weigh 1 g of acrylamide (AM), dissolve it in 5 ml of deionized water, add it to the solution in step 4 at 75°C, and react for 5 minutes.

[0046] S6. Accurately weigh 0.4 g of N-N-methylenebispropylene (MBA), dissolve it in 20 ml of deionized water, add it to the solution in step 5, culture it in water at 65 ° C, and cross-link it for 8 hours. After the reaction is completed, rinse it with deionized water until it is neutral, and dry it at 60 ° C to obtain sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent, which is recorded as SA-EMR. 2∶1 .

[0047] Example 3 A method for preparing a heavy metal adsorbent for acidic antimony mine wastewater comprises the following steps: S1. Accurately weigh 5g of sodium alginate into a beaker, add 40ml of deionized water, place on a magnetic stirrer at 90℃, 30r / min and stir for 30min.

[0048] S2. Accurately weigh 3 g of electrolytic manganese slag and add it to the uniformly gelatinized sodium alginate solution in step 1. Stir at 30 rpm for 15 min. Place the mixture in an ultrasonic cleaner with an ultrasonic power of 200 W and ultrasonicate for 15 min to obtain a uniformly mixed sodium alginate / electrolytic manganese slag solution.

[0049] S3. Accurately weigh 0.1 g of ammonium persulfate (APS) initiator, dissolve it in 2 ml of deionized water, add the sodium alginate / electrolytic manganese slag solution in step 2 at 75°C, and react for 3 minutes.

[0050] S4. Accurately weigh 1g of sodium hydroxide and dissolve it in 10ml of deionized water. Measure 4ml of acrylic acid (AA) and add it to the solution in step 3 at 75°C and react for 5min.

[0051] S5. Accurately weigh 1 g of acrylamide (AM), dissolve it in 5 ml of deionized water, add it to the solution in step 4 at 75°C, and react for 5 minutes.

[0052] S6. Accurately weigh 0.4 g of N-N-methylenebispropylene (MBA), dissolve it in 20 ml of deionized water, add it to the solution in step 5, culture it in water at 65 ° C, and cross-link it for 8 hours. After the reaction is completed, rinse it with deionized water until it is neutral, and dry it at 60 ° C to obtain sodium alginate / electrolytic manganese slag / polyacrylamide adsorbent, which is recorded as SA-EMR. 5∶3 .

[0053] SA-EMR 5∶2 、SA-EMR2∶1 、SA-EMR 5∶3 The swelling properties of the three adsorbents were tested to obtain SA-EMR 5∶2 The swelling rate of SA-EMR is 473.2%. 2∶1 The swelling rate of SA-EMR is 531.9%. 5∶3 The swelling rate of SA-EMR is 140.3%. 2∶1 The swelling property is the best.

[0054] Choose SA-EMR 2∶1 Perform effect verification 1.

[0055] (1) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 12.5mg / L Sb at pH 6. 3+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 20-min intervals. The remaining Sb in the solution was determined by atomic absorption spectrometry. 3+ The ion concentrations are shown in Table 1.

[0056] Table 1: (2) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 25mg / L Sb at pH 6. 3+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 20-min intervals. The remaining Sb in the solution was determined by atomic absorption spectrometry. 3+ The ion concentrations are shown in Table 2 below.

[0057] Table 2: (3) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 50mg / L Sb at pH 6. 3+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 20-min intervals. The remaining Sb in the solution was determined by atomic absorption spectrometry. 3+ The ion concentrations are shown in Table 3 below.

[0058] Table 3: (4) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add pH=2, 250ml, 50mg / L Sb 3+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 20-min intervals. The remaining Sb in the solution was determined by atomic absorption spectrometry.3+ Ion concentration, the results are shown in Table 4 below.

[0059] Table 4: (5) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add pH=3, 250ml, 50mg / L Sb 3+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 20-min intervals. The remaining Sb in the solution was determined by atomic absorption spectrometry. 3+ Ion concentration, the results are shown in Table 5 below.

[0060] Table 5: (6) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add pH=5, 250ml, 50mg / L Sb 3+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 20-min intervals. The remaining Sb in the solution was determined by atomic absorption spectrometry. 3+ Ion concentration, the results are shown in Table 6 below.

[0061] Table 6: Comparison of different adsorbents on Sb 3+ The adsorption effect of ions is shown in Table 7 below.

[0062] Table 7: As shown in Tables 1 to 7 above, the adsorbent prepared by the present invention has a pH of 5, 50 mg / L Sb 3+ In ionic solution, compared with other pH and concentration of Sb 3+ , the adsorption equilibrium was reached in 120 min, and the maximum adsorption capacity was 36.75 mg / g.

[0063] Effect verification 2: (1) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 12.5mg / L Pb at pH 4.5 2+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 60-min intervals. The residual Pb in the solution was determined by atomic absorption spectrometry. 2+ Ion concentration, the results are shown in Table 8 below.

[0064] Table 8: (2) 0.6 g / L SA-EMR2∶1 Adsorbent dosage: Add 250ml of 25mg / L Pb at pH 4.5 2+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 60-min intervals. The residual Pb in the solution was determined by atomic absorption spectrometry. 2+ Ion concentration, the results are shown in Table 9 below.

[0065] Table 9: (3) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 50mg / L Pb at pH 4.5 2+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 60-min intervals. The residual Pb in the solution was determined by atomic absorption spectrometry. 2+ Ion concentration, the results are shown in Table 10 below.

[0066] Table 10: (4) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 100mg / L Pb at pH 4.5 2+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 60-min intervals. The residual Pb in the solution was determined by atomic absorption spectrometry. 2+ Ion concentration, the results are shown in Table 11 below.

[0067] Table 11: (5) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 50mg / L Pb at pH 3.5 2+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 60-min intervals. The residual Pb in the solution was determined by atomic absorption spectrometry. 2+ Ion concentration, the results are shown in Table 12 below.

[0068] Table 12: (6) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 50mg / L Pb at pH 5.5 2+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 60-min intervals. The residual Pb in the solution was determined by atomic absorption spectrometry. 2+ Ion concentration, the results are shown in Table 13 below.

[0069] Table 13: (7) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 50mg / L Pb at pH 6.5 2+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 60-min intervals. The residual Pb in the solution was determined by atomic absorption spectrometry. 2+ Ion concentration, the results are shown in Table 14 below.

[0070] Table 14: (8) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 100mg / L Pb at pH 5.5 2+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 60-min intervals. The residual Pb in the solution was determined by atomic absorption spectrometry. 2+ Ion concentration, the results are shown in Table 15 below.

[0071] Table 15: As shown in Tables 8 to 15 above, the adsorbent prepared by the present invention has a good adsorption performance at pH = 4.5 and 100 mg / L Pb 2 In ion solution, compared with other concentrations of Pb 2 , the adsorption equilibrium was reached in 100 min, and the maximum adsorption capacity was 157.92 mg / g.

[0072] Effect verification 3: (1) 0.6 g / L SA-EMR 2∶1 Adsorbent dosage: Add 250ml of 50mg / L Pb at pH 4.5 2+ ions, 50mg / LSb 3+ The ion solution was placed on a 120 rpm shaker, and samples were taken at 20-min intervals. The residual Pb in the solution was determined by atomic absorption spectrometry. 2+ ions, Sb 3+ Ion concentration, the results are shown in Tables 16 and 17 below.

[0073] Table 16: Table 17: As shown in Tables 16 and 17, when both lead and antimony heavy metal ions are present, the adsorbent preferentially adsorbs trivalent antimony ions, and the maximum adsorption capacity does not decrease significantly compared to a single antimony ion solution. In contrast, when both lead and antimony heavy metal ions are present, the adsorbent's maximum adsorption capacity for lead ions decreases significantly compared to a single lead ion solution. The adsorbent of the present invention is preferably used for selectively adsorbing antimony ions from antimony mine wastewater containing both lead and antimony heavy metal ions. The pH of the acidic antimony mine wastewater is preferably adjusted to 4-6, and the amount of the acidic antimony mine wastewater heavy metal adsorbent added is 0.6-1 g per liter of acidic antimony mine wastewater.

[0074] In summary, the present invention uses Class II general industrial solid waste, electrolytic manganese slag, as a raw material to compound sodium alginate and polyacrylamide, and prepares a highly efficient selective adsorption gel through a simple hydrothermal method. This gel adsorbent overcomes the difficulties of conventional activated electrolytic manganese slag adsorbent powder, which is difficult to separate and recycle, as well as the poor mechanical properties of sodium alginate-based adsorbents. Furthermore, the present invention has excellent adsorption properties for single lead and antimony heavy metal ions, and when two heavy metals are present simultaneously, the composite adsorbent has good selective adsorption properties for trivalent antimony ions. Therefore, the present invention not only provides a new path for the high-value resource utilization of electrolytic manganese slag, but also provides a new material for the adsorption and removal of lead, antimony and heavy metal ions in acidic antimony mine wastewater.

[0075] The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and the specific implementation of the present invention should not be considered to be limited to these descriptions. For those skilled in the art of the present invention, several simple deductions and substitutions can be made without departing from the concept of the present invention, and all of these should be considered to fall within the scope of protection of the present invention.

Claims

1. A method for preparing a heavy metal adsorbent for acidic antimony mine wastewater, characterized in that: The steps include: S1, adding sodium alginate into the aqueous solution, stirring at a constant temperature, to obtain a paste-like uniform sodium alginate aqueous solution; S2, adding electrolytic manganese slag to the sodium alginate aqueous solution, stirring and ultrasonically treating to form a uniform first solution; S3, preparing an ammonium persulfate (APS) initiator solution, adding it to the first solution to obtain a second solution; S4, preparing a sodium hydroxide solution and an acrylic acid (AA) solution, and adding them into the second solution to obtain a third solution; S5, preparing an acrylamide (AM) solution, and adding it into the third solution to obtain a fourth solution; S6, preparing NN methylenebisacrylamide (MBA) solution, and adding it into the fourth solution to obtain a fifth solution; Under the hydroponic condition of 60-65° C., the fifth solution is subjected to a cross-linking reaction. After the cross-linking reaction is completed, the adsorption gel is washed with deionized water until it is neutral and dried to obtain a sodium alginate-electrolytic manganese slag-polyacrylamide adsorbent.

2. The method for preparing a heavy metal adsorbent for acidic antimony mine wastewater according to claim 1, characterized in that: In step S6, the cross-linking reaction time is 8 to 12 hours.

3. The method for preparing a heavy metal adsorbent for acidic antimony mine wastewater according to claim 1, characterized in that: In step S1, the sodium alginate is analytical grade; the mass-to-liquid ratio of the sodium alginate aqueous solution is 5 g:35-45 ml; the stirring temperature is 80-90° C., and the stirring time is 30-40 min.

4. The method for preparing a heavy metal adsorbent for acidic antimony mine wastewater according to claim 1, characterized in that: In the step S2, the stirring ultrasonic treatment includes stirring for 15-20 minutes at a rotation speed of 30 r / min, and ultrasonicating for 15-30 minutes at an ultrasonic power of 200 W; the pretreatment of the electrolytic manganese slag includes: calcining at 400-600° C., crushing and then passing through a 100-mesh sieve to obtain the undersize.

5. The method for preparing a heavy metal adsorbent for acidic antimony mine wastewater according to claim 1, characterized in that: The mass ratio of sodium alginate to electrolytic manganese slag is 5:2-3; the mass ratio of sodium alginate to ammonium persulfate (APS) initiator is 5:0.1-0.15; the mass ratio of sodium alginate to sodium hydroxide is 5:1-1.5; the mass volume ratio of sodium alginate to acrylic acid (AA) is 5g:3-5ml; the mass ratio of sodium alginate to acrylamide (AM) is 5:0.8-1.2; the mass ratio of sodium alginate to NN methylenebispropylene (MBA) is 5:0.3-0.

4.

6. The method for preparing a heavy metal adsorbent for acidic antimony mine wastewater according to claim 1, characterized in that: In the step S3, the temperature when the first solution is added is 75-80°C, and the reaction takes 3-5 minutes after the first solution is added; in the step S4, the temperature when the second solution is added is 75-80°C, and the reaction takes 3-5 minutes after the second solution is added; in the step S5, the temperature when the third solution is added is 75-80°C, and the reaction takes 3-5 minutes after the third solution is added.

7. The method for preparing a heavy metal adsorbent for acidic antimony mine wastewater according to claim 1, characterized in that: In step S6, the drying temperature is 60-80°C.

8. A heavy metal adsorbent for acidic antimony mine wastewater, characterized in that: The heavy metal adsorbent for acidic antimony mine wastewater is prepared by the preparation method of any one of claims 1 to 7.

9. An application of a heavy metal adsorbent for acidic antimony mine wastewater, characterized in that: The heavy metal adsorbent for acidic antimony mine wastewater is the heavy metal adsorbent for acidic antimony mine wastewater as claimed in claim 8, which is used to remove heavy metals such as lead and antimony in acidic antimony mine wastewater.

10. The use of the heavy metal adsorbent for acidic antimony mine wastewater according to claim 9, characterized in that: First, the pH value of the acidic antimony mine wastewater is adjusted to 4-6, and the amount of the heavy metal adsorbent for acidic antimony mine wastewater added to each liter of the acidic antimony mine wastewater is 0.6-1 g.

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