A method for removing gelatin-like organic matter from waste electrolyte in hydrometallurgical zinc smelting process

Abstract

The present invention belongs to the technical field of hydrometallurgy, specifically a method for removing gelatin-like organic matter from waste electrolyte during hydrometallurgy. The method comprises mixing the waste electrolyte from the hydrometallurgy process containing gelatin with modified A885817 activated carbon, performing oscillatory adsorption, and then performing solid-liquid separation. The preparation method of the modified A885817 activated carbon comprises modifying the A885817 activated carbon with an H2SO4 solution, washing with water until neutral, and then drying. This method can rapidly adsorb various organic matter. It has the advantages of a wide range of applications, short adsorption time, simple operation, and excellent adsorption performance. It effectively removes organic matter and reduces TOC (total organic carbon) content during the hydrometallurgy process.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrometallurgy zinc smelting, and in particular relates to a method for removing gelatinous organic matter from waste electrolyte in a hydrometallurgy zinc smelting process. Background Art

[0002] Zinc is an important nonferrous metal widely used in galvanizing materials, zinc alloys, and zinc batteries. Sphalerite is the primary mineral in zinc smelting, and hydrometallurgy is the most commonly used smelting process, with pyrometallurgy accounting for only approximately 20% of zinc production. The traditional hydrometallurgical zinc smelting process includes roasting, leaching, purification, and electrodeposition. Direct leaching omits the roasting step and consists solely of leaching, purification, and electrodeposition. The smelting process involves a variety of organic substances, such as flotation agents, flocculants, metal extractants, and electrolytic additives. These organic substances enter the smelting system through flotation, purification, and electrolytic deposition. While roasting removes most organic matter from the ore, the liquids produced by silver flotation, extraction, and electrolytic deposition are not roasted. Therefore, residual organic matter from roasting, silver flotation agents, extractants, and electrolytic additives accumulate in the smelting system. These organic substances are numerous, with diverse sources and properties, complex behaviors, and unclear mechanisms of action. They can negatively impact the hydrometallurgical zinc smelting process, particularly zinc electrolytic deposition. Currently, the total organic carbon (TOC) content in fresh electrolytic solution is high, leading to issues in the electrolytic deposition process, such as plate burning, poor zinc flake quality, and difficulty in mechanized zinc stripping. Therefore, it is necessary to further investigate the sources of organic matter and improve the adsorption efficiency of activated carbon. Currently, one of the most difficult organic matter to decompose is bone glue.

[0003] Methods for removing organic matter include activated carbon adsorption, oxidative degradation, flotation, membrane separation, coagulation, and biological methods. Currently, adsorption is the primary method for removing organic matter from electrolytes in industry. The most widely used adsorption aid in this adsorption method is activated carbon. Activated carbon adsorbs organic matter (oils, additives, etc.) primarily through physical adsorption. Because activated carbon's porous structure creates a large surface area, the molecular forces of attraction between them create a strong attraction, attracting small molecules into the pores and removing them. Activated carbon adsorption requires a large amount of activated carbon to adsorb the liquid. In actual processes, the activated carbon remains in the process for a very short time, resulting in incomplete adsorption and significantly reducing its effectiveness. When the smelting system temperature is around 45-90°C, the activated carbon's active sites become inactivated, weakening its adsorption capacity. Summary of the Invention

[0004] In response to the shortcomings of the existing technology, the present invention provides a method for removing gelatin-like organic matter from waste electrolyte in the hydrometallurgical zinc smelting process, which can reduce the TOC (Total Organic Carbon), especially the gelatin content, in the waste electrolyte in the hydrometallurgical zinc smelting process, improve the quality of the electrolyte, and significantly increase the removal rate of organic matter.

[0005] A method for removing gelatin-like organic matter from waste electrolyte in a hydrometallurgical zinc smelting process comprises: mixing the waste electrolyte from the hydrometallurgical zinc smelting process containing gelatin with modified A885817 activated carbon, performing oscillation adsorption, and then performing solid-liquid separation. The preparation method of the modified A885817 activated carbon comprises: subjecting the A885817 activated carbon to a modification reaction with an H2SO4 solution, washing with water to neutrality, and then drying. The concentration of the H2SO4 solution is 0.5-2 mol / L, and the ratio of the A885817 activated carbon to the H2SO4 solution is 1 g: (5-20) mL.

[0006] The inventors have discovered that A885817 activated carbon can effectively remove organic matter, particularly gelatin, from waste electrolytes from the hydrometallurgical zinc smelting process. This activated carbon achieves an adsorption rate of over 90% for organic matter in waste electrolytes from the hydrometallurgical zinc smelting process, significantly reducing the organic matter content. Other types of activated carbon have poor adsorption effects on organic matter, particularly gelatin.

[0007] The method of the present invention has the advantages of wide application range, short adsorption time, simple operation and high accuracy in adsorbing organic matter.

[0008] In some embodiments, the specific surface area of ​​the A885817 activated carbon is 956.78-1399.647 m 2 / g, particle size is 200-400 mesh, pore size is 2.22-4.25nm, and iodine value is 800-1300 mg / g.

[0009] The A885817 activated carbon described in the present invention can be purchased commercially from Shanghai MacLean Biochemical Technology Co., Ltd.

[0010] Preferably, the content of bone glue in the waste electrolyte of the hydrometallurgical zinc smelting process is 500-2000 mg / L.

[0011] The content of bone glue in the spent electrolyte of the hydrometallurgical zinc smelting process can be detected by conventional methods in the prior art (such as ultraviolet-visible spectrophotometry, UV-Vis).

[0012] Experiments have shown that the method of the present invention can reduce the content of gelatin in the waste electrolyte of the wet zinc smelting process to 20 ppm, which is 80-99% lower than that before adsorption.

[0013] Preferably, the ratio of the modified A885817 activated carbon to the waste electrolyte from the hydrometallurgical zinc smelting process is (0.01g-1g):100mL, more preferably 1g:100mL.

[0014] Within this range of activated carbon dosage, the bone glue can be better adsorbed, thereby helping to improve the removal rate.

[0015] Preferably, the oscillation speed of the oscillatory adsorption is 80-160 r / min, more preferably 120 r / min. Within this oscillation speed range, the removal rate of bone glue can be improved.

[0016] Preferably, the oscillation adsorption temperature is 25° C.-65° C., more preferably 65° C. The present invention has found that temperature has a significant effect on the removal rate of bone glue. The oscillation temperature range can be conducive to improving the removal rate of bone glue.

[0017] Typically, the oscillation time (i.e., the activated carbon adsorption time) is 0.5 h to 4 h, more preferably 2 h. Compared with using other types of activated carbon, the treatment time is significantly reduced.

[0018] In a preferred embodiment of the present invention, in the method for removing gelatinous organic matter from the waste electrolyte of the hydrometallurgical zinc smelting process, the ratio of the modified A885817 activated carbon to the waste electrolyte of the hydrometallurgical zinc smelting process is (0.01g-1g):100mL, the oscillation speed during the oscillation adsorption is 80-160r / min; the temperature of the oscillation adsorption is 25-65°C; and the time of the oscillation adsorption is 0.5h-4h.

[0019] In a further preferred embodiment of the present invention, in the method for removing gelatinous organic matter from waste electrolyte from a zinc hydrometallurgy process, the ratio of modified A885817 activated carbon to waste electrolyte from a zinc hydrometallurgy process is 1 g:100 mL, the oscillation speed during the oscillation adsorption is 120 r / min, the temperature for the oscillation adsorption is 65°C, and the oscillation adsorption time is 2 hours. Conventional separation methods (such as sand filtration) can typically be used to separate the adsorbed liquid into solids and liquids.

[0020] In the method of the present invention, the A885817 activated carbon has excellent specificity for adsorbing bone glue in the waste electrolyte of the hydrometallurgical zinc smelting process.

[0021] Conventional activated carbon adsorption methods are mostly based on small-scale laboratory simulations, and the experimental results often differ from actual industrial applications. Furthermore, they suffer from issues such as being time-consuming, requiring large amounts of activated carbon, insufficient mixing, incomplete reaction, and being unsuitable for large-scale adsorption.

[0022] Experiments have shown that the method of the present invention can effectively remove gelatinous organic matter from waste electrolyte in the wet zinc smelting process.

[0023] If necessary, conventional methods such as infrared analysis can be used to qualitatively analyze the organic matter in the waste electrolyte of the hydrometallurgical zinc smelting process. If it is determined that the waste electrolyte of the hydrometallurgical zinc smelting process contains gelatin (for example, within the above content range) based on its functional groups, the method of the present invention can be used for adsorption treatment.

[0024] The present inventors unexpectedly discovered that modifying A885817 activated carbon can significantly reduce its usage without affecting the adsorption effect on bone glue.

[0025] Preferably, the temperature of the modification reaction is 25-65°C.

[0026] Preferably, the modification reaction time is 0.5-24 hours.

[0027] In some specific embodiments, the preparation method of the modified A885817 activated carbon includes: mixing A885817 activated carbon and 0.5 mol / L H2SO4 solution in a ratio of 1 g:10 mL, modifying at 25°C for 2 hours, then washing with pure water to neutrality, and drying (for example, baking in a 45°C oven for 24 hours) to obtain modified A885817 activated carbon.

[0028] The present invention also provides modified A885817 activated carbon obtained by the above method.

[0029] Experiments show that compared with unmodified A885817 activated carbon, the adsorption rate of bone glue by the modified A885817 activated carbon is close to 60% when the dosage is reduced to 2% of the original dosage; when the solid-liquid ratio (mg / mL) of the modified A885817 activated carbon to the waste electrolyte is 10:1, the adsorption rate of bone glue reaches 95.24%.

[0030] The waste electrolyte of the hydrometallurgical zinc smelting process mentioned in the present invention refers to the solution produced after various processes in the hydrometallurgical zinc smelting process such as leaching, purification, and electrolysis.

[0031] In some specific embodiments, the waste electrolyte of the hydrometallurgical zinc smelting process is waste electrolyte of zinc smelting plant with different metal ion concentrations, including Zn 2+ 、Na 2+ 、Cu 2+ Mg 2+ , K + 、Mn 2+ and Ca 2+ .

[0032] In some specific embodiments, the waste electrolyte of the hydrometallurgical zinc smelting process is waste liquid generated by the electrolysis process of a zinc smelter, wherein the Zn concentration is 30-80 g / L and the H2SO4 concentration is 120-210 g / L (e.g., 150-180 g / L).

[0033] The method of the present invention has the following advantages and positive effects:

[0034] Existing adsorption methods rely on simulated experiments on the feed solution, which is time-consuming and labor-intensive. Simulated feed solutions are less complex than on-site production, making them unsuitable for large-scale adsorption. Short adsorption times can lead to incomplete adsorption. The method of the present invention can rapidly adsorb various organic substances (especially bone glue). This method has the advantages of a wide range of applicability, short adsorption time, simple operation, and excellent adsorption effectiveness. It effectively removes organic matter and reduces TOC content during the hydrometallurgical zinc smelting process.

[0035] The method of the present invention can be promoted and applied in zinc smelters to improve the quality of electrolyte and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 These are the infrared spectra of activated carbon before and after adsorption of waste electrolyte before and after modification. DETAILED DESCRIPTION

[0037] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0038] The following activated carbons are numbered 1 # , 2 # , 3 # , 4 # , 5 # , 6 # , 7 # , 8 # , 9 # .

[0039] 1 # It is a coal-based cylindrical solid activated carbon with a specific surface area of ​​10.347-14.566m 2 / g, particle size is 3.95-4.05mm, and pore size is 5.34-5.59nm.

[0040] 2 # It is a coal-based columnar solid activated carbon with a specific surface area of ​​608.789-795.456m 2 / g, particle size is 1.45-1.55mm, pore size is 2.13-2.27nm, and iodine value is 1050-1150mg / g.

[0041] 3 #A885817 activated carbon (purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) with a specific surface area of ​​956.78-1399.647 m 2 / g, particle size is 200-400 mesh, pore size is 2.22-4.25nm, and iodine value is 800-1300 mg / g.

[0042] 4 # It is coal-based granular solid activated carbon with a specific surface area of ​​756.113-983.846m 2 / g, pore size is 2.03-2.29nm.

[0043] 5 # It is a wood fine granular solid activated carbon with a specific surface area of ​​135.447-258.257m 2 / g, particle size is 40-60mm, pore size is 3.13-3.37nm, and iodine value is 900-1100mg / g.

[0044] 6 # It is a solid activated carbon in the form of wood crushed blocks with a specific surface area of ​​34.983-52.233m 2 / g, particle size is 10-24mm.

[0045] 7 # It is a wooden cylindrical solid activated carbon with a specific surface area of ​​16.062-53.556m 2 / g, particle size is 5.95-6.25mm, and pore size is 8.13-8.37nm.

[0046] 8 # It is a wood block solid activated carbon with a specific surface area of ​​23.998-65.221m 2 / g, particle size is 6-12mm, and pore size is 2.12-2.28nm.

[0047] 9 # It is wood powder activated carbon with a specific surface area of ​​633.188-879.442m 2 / g, and the pore size is 2.17-2.28nm.

[0048] The following method for analyzing organic matter in the spent electrolyte and post-adsorption solution from the hydrometallurgical zinc smelting process is a combination of infrared spectroscopy analysis of the solution before and after adsorption, and ultraviolet spectrophotometry and total organic carbon instrument detection. The adsorption of organic matter is confirmed by changes in functional groups, adsorption rate, and TOC value.

[0049] The following absorbance determination method is to set the organic matter in the solution as 100% as a whole, and then establish a standard curve for the solution at a specific wavelength by diluting the solution to different concentration gradients.

[0050] Calculation method of adsorption rate:

[0051] ;

[0052] Where η is the adsorption rate, q 吸 is the adsorption amount, and q0 is the content of organic matter before adsorption.

[0053] The following method for analyzing TOC in the spent electrolyte and post-adsorption liquid during the hydrometallurgical zinc smelting process is to perform TOC detection using a total organic carbon instrument. The total carbon minus the inorganic carbon is the organic matter content.

[0054] Example 1

[0055] Waste electrolyte from hydrometallurgical zinc smelting in a domestic zinc smelter contains: Zn 2+ 50.23 g / L, Na 2+ 20.57 g / L, Cu 2+ 40.88 mg / L, Mg 2+ is 17.14 g / L, K + 3.45 g / L, Mn 2+ 2.13 g / L, Ca 2+ It is 252.46 mg / L.

[0056] Analysis of the spent electrolyte revealed the following main functional groups: CO, C=C, -OH, and CH. Bone glue, added during the electrolytic deposition process in the zinc smelting system, was analyzed by infrared spectroscopy and revealed the following main functional groups: COC, C=C, and -OH. These functional groups are similar to those found in the spent electrolyte.

[0057] The absorbance of the waste electrolyte was detected, and the result was: 0.760 Abs.

[0058] The TOC test result of the waste electrolyte was 49.26 mg / L.

[0059] This embodiment provides a method for removing gelatinous organic matter from waste electrolyte in a hydrometallurgical zinc smelting process, comprising the following steps: adding 100 mL of the waste electrolyte and A885817 activated carbon (3 # ) 0.5g; oscillate in a constant temperature water bath at a speed of 120r / min, while the temperature is raised to 65°C; react for 0.5h; perform sand filtration using a 0.45μm water filter membrane for solid-liquid separation to obtain the adsorbed liquid.

[0060] The post-adsorption liquid was analyzed and the results were as follows: the main functional groups were: -OH, CO, C=C, CH. The results showed that the functional groups of the post-adsorption liquid in the waste electrolyte were weakened by infrared spectrometry.

[0061] A885817 activated carbon (3 # ) are replaced with the above 1 # , 2 # , 4 # , 5 # , 6 # , 7 # , 8 # , 9 # Activated carbon.

[0062] The absorbance of the adsorbed liquid was detected, and the results were as follows: 1 # :0.755 Abs;2 # :0.733 Abs;3 # :0.388Abs;4 # :0.508 Abs;5 # :0.528 Abs;6 # :0.541 Abs;7 # :0.756 Abs;8 # :0.442 Abs;9 # :0.436Abs.

[0063] It can be seen that A885817 activated carbon has the best adsorption effect, with an adsorption rate of 49.00%.

[0064] The TOC test results of the adsorbed liquid are as follows: 1 # :37.21 mg / L; 2 # :35.11 mg / L; 3 # :19.013mg / L;4 # :27.88 mg / L;5 # :38.35 mg / L;6 # :40.71 mg / L;7 # :38.78 mg / L;8 # :39.78 mg / L;9 # :21.14 mg / L.

[0065] It can be seen that A885817 activated carbon has the best adsorption effect, and TOC is reduced by 61.40% on the original basis.

[0066] The adsorption efficiency of organic matter showed that the adsorption requirements were met. The A885817 activated carbon had a significant effect on adsorbing bone glue.

[0067] Example 2

[0068] Waste electrolyte from a domestic zinc smelter contains: Zn 2+ 56.31 g / L, Na 2+12.26 g / L, Mg 2+ 10.44 g / L, K + 3.79 g / L, Mn 2+ 2.16 g / L, Ca 2+ It is 270.78 mg / L.

[0069] Analysis of the spent electrolyte revealed the following main functional groups: CO, C=C, -OH, and CH. Bone glue, added during the electrolytic deposition process in the zinc smelting system, was analyzed by infrared spectroscopy and revealed the following main functional groups: COC, C=C, and -OH. These functional groups are similar to those found in the spent electrolyte.

[0070] The absorbance of the waste electrolyte was detected, and the result was: 0.768 Abs.

[0071] The waste electrolyte was tested for TOC, and the result was: TOC was 48.75 mg / L.

[0072] This embodiment provides a method for removing gelatinous organic matter from waste electrolyte in a hydrometallurgical zinc smelting process, comprising the following steps: adding 100 mL of the waste electrolyte and A885817 activated carbon (3 # ) 0.5g; oscillate in a constant temperature water bath at a speed of 120r / min, while the temperature is raised to 65℃; react for 0.5h; perform sand filtration with a 0.45μm water filter membrane for solid-liquid separation to obtain the adsorbed liquid.

[0073] The post-adsorption liquid was analyzed and the results were as follows: the main functional groups were: CO, C=C, -OH, CH. The results showed that the functional groups of the post-adsorption liquid in the waste electrolyte were weakened by infrared spectrometry.

[0074] A885817 activated carbon (3 # ) are replaced with the above 1 # , 2 # , 4 # , 5 # , 6 # , 7 # , 8 # , 9 # Activated carbon.

[0075] The absorbance of the adsorbed liquid was detected, and the results were as follows: 1 # :0.662 Abs; 2 # :0.528 Abs; 3 # :0.405Abs; 4 # :0.533 Abs; 5 # :0.492 Abs; 6 #:0.441 Abs; 7 # :0.456 Abs; 8 # :0.421 Abs;9 # :0.567Abs.

[0076] Therefore, A885817 activated carbon has the best adsorption effect, with an adsorption rate of 47.31%.

[0077] The TOC test results of the adsorbed liquid are as follows: 1 # :35.98 mg / L; 2 # :32.25 mg / L; 3 # :21.05 mg / L; 4 # :29.91 mg / L; 5 # :35.13 mg / L; 6 # :46.84 mg / L; 7 # :33.79 mg / L; 8 # :39.23 mg / L; 9 # :31.31 mg / L.

[0078] A885817 activated carbon had the best adsorption effect, with TOC reduced by 56.82% from the original level.

[0079] The adsorption efficiency of organic matter showed that the adsorption requirements were met. The A885817 activated carbon had a significant effect on adsorbing bone glue.

[0080] Example 3

[0081] Waste electrolyte from a domestic zinc smelter contains: Zn 2+ 60.34 g / L, Na 2+ 15.35 g / L, Mg 2+ is 13.67 g / L, K + 3.13 g / L, Mn 2+ 2.18 g / L, Ca 2+ It is 275.66 mg / L.

[0082] Analysis of the spent electrolyte revealed the following main functional groups: CO, C=C, -OH, and CH. Bone glue, added during the electrolytic deposition process in the zinc smelting system, was analyzed by infrared spectroscopy and revealed the following main functional groups: COC, C=C, and -OH. These functional groups are similar to those found in the spent electrolyte.

[0083] The absorbance of the waste electrolyte was detected, and the result was: 0.778 Abs.

[0084] The waste electrolyte was tested for TOC, and the result was: TOC was 39.88 mg / L.

[0085] This embodiment provides a method for removing gelatinous organic matter from waste electrolyte in a hydrometallurgical zinc smelting process, comprising the following steps: adding 100 mL of the waste electrolyte of this embodiment and A885817 activated carbon (3 # ) 0.5g; oscillate in a constant temperature water bath at a speed of 120r / min, while the temperature is raised to 65℃; react for 0.5h; perform sand filtration with a 0.45μm water filter membrane for solid-liquid separation to obtain the adsorbed liquid.

[0086] The post-adsorption liquid was analyzed and the results were as follows: the main functional groups were: CO, C=C, -OH, CH. The results showed that the functional groups of the post-adsorption liquid in the waste electrolyte were weakened by infrared spectrometry.

[0087] A885817 activated carbon (3 # ) are replaced with the above 1 # , 2 # , 4 # , 5 # , 6 # , 7 # , 8 # , 9 # Activated carbon.

[0088] The absorbance of the adsorbed liquid was detected, and the results were as follows: 1 # :0.626 Abs; 2 # :0.511 Abs; 3 # :0.427 Abs; 4 # :0.495 Abs; 5 # :0.593 Abs; 6 # :0.498 Abs; 7 # :0.452 Abs; 8 # :0.498Abs; 9 # :0.518Abs.

[0089] Therefore, A885817 activated carbon has the best adsorption effect, with an adsorption rate of 45.16%.

[0090] The TOC test results of the adsorbed liquid are as follows: 1 # : 34.98 mg / L; 2 # : 35.25 mg / L; 3 # :28.78 mg / L;4 # :24.913 mg / L; 5 # :35.16 mg / L;6# :32.84 mg / L;7 # : 33.73 mg / L; 8 # : 36.22mg / L; 9 # : 33.31 mg / L.

[0091] A885817 activated carbon had the best adsorption effect, with TOC reduced by 27.83% from the original level.

[0092] The adsorption efficiency of organic matter showed that the adsorption requirements were met. The A885817 activated carbon had a significant effect on adsorbing bone glue.

[0093] Example 4

[0094] Waste electrolyte from a domestic zinc smelter contains: Zn 2+ 69.12 g / L, Na 2+ 16.44 g / L, Mg 2+ is 17.68 g / L, K + 3.57 g / L, Mn 2+ 1.28 g / L, Ca 2+ It is 214.76 mg / L.

[0095] Analysis of the spent electrolyte revealed the following main functional groups: CO, C=C, -OH, and CH. Bone glue, added during the electrolytic deposition process in the zinc smelting system, was analyzed by infrared spectroscopy and revealed the following main functional groups: COC, C=C, and -OH. These functional groups are similar to those found in the spent electrolyte.

[0096] The absorbance of the waste electrolyte was detected, and the result was: 0.764 Abs.

[0097] The waste electrolyte was tested for TOC, and the result was: TOC was 40.26 mg / L.

[0098] This embodiment provides a method for removing gelatinous organic matter from waste electrolyte in a hydrometallurgical zinc smelting process, comprising the following steps: adding 100 mL of the waste electrolyte of this embodiment and A885817 activated carbon (3 # ) 0.5g; oscillate in a constant temperature water bath at a speed of 120r / min, while the temperature is raised to 65℃; react for 0.5h; perform sand filtration with a 0.45μm water filter membrane for solid-liquid separation to obtain the adsorbed liquid.

[0099] The post-adsorption liquid was analyzed and the results were as follows: the main functional groups were: CO, C=C, -OH, CH. The results showed that the functional groups of the post-adsorption liquid in the waste electrolyte were weakened by infrared spectrometry.

[0100] A885817 activated carbon (3# ) are replaced with the above 1 # , 2 # , 4 # , 5 # , 6 # , 7 # , 8 # , 9 # Activated carbon.

[0101] The absorbance of the adsorbed liquid was detected, and the results were as follows: 1 # :0.660 Abs;2 # :0.598 Abs;3 # :0.464Abs;4 # :0.497 Abs;5 # :0.661 Abs;6 # :0.557 Abs;7 # :0.641 Abs;8 # :0.375 Abs;9 # :0.487Abs.

[0102] Therefore, A885817 activated carbon has the best adsorption effect, with an adsorption rate of 39.31%.

[0103] The TOC test results of the adsorbed liquid are as follows: 1 # :39.42 mg / L; 2 # :37.84 mg / L;3 # :31.44mg / L;4 # :35.44 mg / L; 5 # :34.82 mg / L;6 # :37.30 mg / L;7 # :38.22 mg / L;8 # :36.16 mg / L;9 # :34.31mg / L.

[0104] A885817 activated carbon had the best adsorption effect, with TOC reduced by 21.91% from the original level.

[0105] The adsorption efficiency of organic matter showed that the adsorption requirements were met. The A885817 activated carbon had a significant effect on adsorbing bone glue.

[0106] Example 5

[0107] Modify A885817 activated carbon by weighing 10 g of A885817 activated carbon into a conical flask, adding 100 mL of a 0.5 mol / L H2SO4 solution, and modifying the carbon at 25°C for 2 hours. Wash the activated carbon with pure water until neutral and dry it in a 45°C oven for 24 hours to obtain the modified A885817 activated carbon. Finally, place the carbon in a sealed bag.

[0108] This example provides a method for removing gelatin-like organic matter from waste electrolyte during the hydrometallurgical zinc smelting process. The waste electrolyte was treated using the same method as in Example 1, using 0.01 g of the modified A885817 activated carbon and 100 mL of the waste electrolyte. The electrolyte was shaken in a constant-temperature water bath at a speed of 120 r / min while the temperature was raised to 65°C. The reaction was continued for 0.5 h. Sand filtration was performed using a 0.45 μm aqueous filter membrane for solid-liquid separation to obtain an adsorbed liquid.

[0109] The absorbance of the adsorbed solution was measured and the result was 0.324 Abs. Therefore, the adsorption rate was 57.93%.

[0110] The TOC test result of the adsorbed liquid was 23.18 mg / L, which was a 52.94% reduction from the original level.

[0111] Compared with Example 1, when the dosage of modified A885817 activated carbon is reduced to 2% of the original dosage, the adsorption effect on bone glue is close to that in Example 1, indicating that the modified A885817 activated carbon has a better adsorption effect on bone glue.

[0112] Example 6

[0113] This example provides a method for removing gelatinous organic matter from waste electrolyte during the hydrometallurgical zinc smelting process, using the same modified A885817 activated carbon as in Example 5. This example differs from Example 5 only in that the oscillating adsorption temperature is changed to 25°C, 35°C, 45°C, and 55°C, respectively.

[0114] The adsorption results are shown in Table 1 below.

[0115] Table 1 Adsorption rate of waste electrolyte at different temperatures

[0116]

[0117] Note: The stock solution in Table 1 refers to the spent electrolyte (without adsorbed bone gelatin). The absorbance may fluctuate slightly between measurements (error). The same applies below.

[0118] Example 7

[0119] This example provides a method for removing gelatinous organic matter from waste electrolyte during a hydrometallurgical zinc smelting process, utilizing the same modified A885817 activated carbon as in Example 5. This example differs from Example 5 only in that the oscillation speed during oscillatory adsorption is varied to 20 rpm, 40 rpm, 80 rpm, and 160 rpm, respectively.

[0120] The adsorption results are shown in Table 2 below.

[0121] Table 2 Adsorption rate of waste electrolyte at different oscillation speeds

[0122]

[0123] Example 8

[0124] This example provides a method for removing gelatinous organic matter from waste electrolyte during the hydrometallurgical zinc smelting process, using the same modified A885817 activated carbon as in Example 5. This example differs from Example 5 only in that the oscillation adsorption time is changed to 1 hour, 2 hours, 4 hours, 6 hours, and 8 hours, respectively.

[0125] The adsorption results are shown in Table 3 below.

[0126] Table 3 Adsorption rate of waste electrolyte at different times

[0127]

[0128] Example 9

[0129] This example provides a method for removing gelatinous organic matter from waste electrolyte during a zinc hydrometallurgy process, utilizing the same modified A885817 activated carbon as in Example 5. This example differs from Example 5 solely in that the solid-to-liquid ratio during oscillatory adsorption (i.e., the mass ratio of the modified A885817 activated carbon to the volume ratio of the waste electrolyte, measured in mg / mL) was varied to 1:5, 1:1, 5:1, and 10:1, respectively.

[0130] The adsorption results are shown in Table 4 below.

[0131] Table 4 Adsorption rate of waste electrolyte at different solid-liquid ratios

[0132]

[0133] As shown in Examples 5-9, the modified A885817 activated carbon was used to study the adsorption of waste electrolyte. The optimal process conditions were determined by examining the effects of temperature, oscillation speed, time, and solid-to-liquid ratio on the activated carbon's adsorption performance. Tables 1, 2, 3, and 4 show that the optimal experimental conditions for adsorption experiments using waste electrolyte solutions were: adsorption temperature of 65°C, oscillation speed of 120 r / min, adsorption time of 2 h, and a solid-to-liquid ratio (mg / mL) of 10:1. The study found that the main factors influencing the adsorption performance of waste electrolyte were oscillation speed and solid-to-liquid ratio. The adsorption rate was 95.24%, indicating that the modified activated carbon had a superior adsorption effect on gelatin in waste electrolyte. Compared to the adsorption performance of unmodified activated carbon, the adsorption rate increased by 46.24%. Waste electrolytes contain complex components, making adsorption more difficult. When the modified activated carbon of the present invention was used to adsorb gelatin from waste electrolytes, the adsorption rate was similar to that of gelatin from pure gelatin solutions.

[0134] Experiment 1

[0135] The infrared spectra of activated carbon before and after adsorption of waste electrolyte are shown in Figure 2. Figure 1 .from Figure 1 It can be found that the modified activated carbon of Example 5 has increased C=C, COC and CO functional groups, which can better promote the adsorption of waste electrolyte by activated carbon. From the spectrum after adsorption, at 3418.61 cm -1 -NH2 stretching vibration is enhanced at 2862.35cm -1 -CH2 stretching vibration is enhanced at 2551.34 cm -1 The C≡C stretching vibration is enhanced at 1637.27 cm -1 The C=C stretching vibration is weakened at 1060.75 cm -1 The COC stretching vibration is enhanced at 1241.95 cm -1 The C(O)-O stretching vibration is enhanced at 670.37 cm -1 =CH stretching vibration is enhanced at these locations. The presence of peaks from the spent electrolyte at these locations indicates that the activated carbon effectively adsorbs the spent electrolyte at these sites. This suggests that the modified A885817 activated carbon has a better adsorption effect on bone glue.

[0136] Waste electrolyte has a high zinc content and is a high-salt and high-acid solution with a sulfuric acid concentration of 150-180g / L. It also contains a variety of organic matter, especially bone glue, which has a lot of organic residues. ICP analysis of the waste electrolyte shows that the metal ion content is very high, among which Zn 2+ 50-80g / L, Na 2+ 15-30g / L, Cu 2+ 40.88 mg / L, Mg2+ is 17.14 g / L, K + 3.45 g / L, Mn 2+ 2.13 g / L, Ca 2+ The concentration of 252.46 mg / L was observed. Infrared spectroscopy analysis of the spent electrolyte revealed the main functional groups to be CO, C=C, -OH, and CH. Bone glue, added during the electrolytic deposition process in the zinc smelting system, was analyzed by infrared spectroscopy and revealed the main functional groups to be COC, C=C, and -OH. The spectrum contained functional groups that matched those of bone glue, suggesting that the solution contained organic matter.

[0137] Current activated carbon has a poor adsorption effect on complex solutions like spent electrolytes, and the amount of activated carbon required is high. Changing the amount of activated carbon used reduces the adsorption efficiency of organic matter. Using such high amounts of activated carbon is not practical in factory production. Therefore, it is necessary to modify the activated carbon to reduce its dosage and improve its adsorption performance.

[0138] CN115404353A discloses a method for improving the adsorption efficiency of organic matter in zinc hydrometallurgy, which is to modify activated carbon by high-temperature calcination. Under ultrasonic strengthening conditions, the adsorption rate of organic matter in the wet zinc smelting solution can only be increased by 6-8% under the same activated carbon dosage conditions. The present invention is aimed at the adsorption of bone glue in waste electrolyte. The adsorption of bone glue is very difficult. After modification, the adsorption rate of A885817 activated carbon is increased by more than 46%, and the adsorption effect is greatly improved. CN110306063A discloses a method for removing organic matter from tannic acid-precipitated germanium solution in a wet zinc smelting system. Tannic acid in the solution is adsorbed by adding hydrogen peroxide to decompose organic matter once, slurrying, oxidation, secondary organic matter decomposition, purification and adsorption, and the activated carbon dosage during adsorption is 2-4kg / m 3 , the removal rate reached 77.42%. The present invention is aimed at the adsorption of bone glue in waste electrolyte. The adsorption of bone glue is very difficult. The dosage of activated carbon added when the modified A885817 activated carbon is adsorbed is 0.0625kg / m 3 , and the experimental steps are fewer, and the adsorption rate can reach more than 95%. CN102206752A discloses a method for removing organic matter from the supernatant solution of wet zinc smelting with activated carbon. For the organic matter such as xanthate and flocculant remaining in the supernatant, two different types of activated carbon are added in the latter two purification processes for adsorption research. Finally, the adsorption rate reaches 75%. What it adsorbs is the purified liquid with an acidity of only 10g / L. The present invention is aimed at the adsorption of gelatin in waste electrolyte. The adsorption of gelatin is very difficult. The modified A885817 activated carbon is only added once in the solution. The process is simple, and the adsorption rate can reach more than 95%. Therefore, the modified A885817 activated carbon used in the present invention has a certain effect on the adsorption of gelatin in waste electrolyte and is worthy of promotion.

[0139] Although the present invention has been described in detail above using general explanations, specific embodiments, and experiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the present invention. Therefore, such modifications and improvements, which do not depart from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A method for removing gelatinous organic matter from waste electrolyte in a hydrometallurgical zinc smelting process, characterized in that: include: The spent electrolyte from the hydrometallurgical zinc smelting process containing bone glue was mixed with modified A885817 activated carbon and subjected to oscillation adsorption. Then the solid and liquid are separated; The preparation method of the modified A885817 activated carbon comprises: modifying the A885817 activated carbon with an H2SO4 solution, washing with water until neutral, and then drying; the concentration of the H2SO4 solution is 0.5-2 mol / L; the ratio of the A885817 activated carbon to the H2SO4 solution is 1 g: (5-20) mL; The content of bone glue in the waste electrolyte of the hydrometallurgical zinc smelting process is 500-2000 mg / L; The waste electrolyte of the hydrometallurgical zinc smelting process is the waste liquid generated by the electrolysis process of the zinc smelter, wherein the Zn concentration is 30-80 g / L and the H2SO4 concentration is 120-210 g / L; The ratio of the modified A885817 activated carbon to the waste electrolyte of the hydrometallurgical zinc smelting process is (0.01g-1g):100mL; The oscillation speed of the oscillation adsorption is 80-160 r / min; the temperature of the oscillation adsorption is 25° C.-65° C.; and the time of the oscillation adsorption is 0.5 h-4 h.

2. The method for removing gelatinous organic matter from waste electrolyte in a hydrometallurgical zinc smelting process according to claim 1, characterized in that: The ratio of the modified A885817 activated carbon to the waste electrolyte of the hydrometallurgical zinc smelting process is 1 g:100 mL, the oscillation speed of the oscillation adsorption is 120 r / min; the temperature of the oscillation adsorption is 65° C.; and the time of the oscillation adsorption is 2 h.

3. The method for removing gelatinous organic matter from waste electrolyte in a hydrometallurgical zinc smelting process according to claim 1 or 2, characterized in that: In the preparation method of the modified A885817 activated carbon, the temperature of the modification reaction is 25-65° C.; and the time of the modification reaction is 0.5-24 h.

4. The method for removing gelatinous organic matter from waste electrolyte in a hydrometallurgical zinc smelting process according to claim 1 or 2, characterized in that: The preparation method of the modified A885817 activated carbon includes: mixing the A885817 activated carbon and a 0.5 mol / L H2SO4 solution at a ratio of 1 g:10 mL, modifying the mixture at 25°C for 2 hours, then washing the mixture with pure water until neutral, and drying the mixture to obtain the modified A885817 activated carbon.

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