CN111807481B - Treatment method of cyaniding gold extraction wastewater - Google Patents
Treatment method of cyaniding gold extraction wastewater Download PDFInfo
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Abstract
The invention discloses a method for treating cyaniding gold extraction wastewater, which comprises the steps of preparing a silicon-based acid solution by using sodium silicate and a hydrochloric acid solution; preparing aluminum-containing wastewater from aluminum chloride and gold extraction cyanide wastewater; preparing cyaniding gold-extracting silicon-aluminum-containing acidic water by using a silicon-based acid solution and cyaniding gold-extracting aluminum-containing wastewater; performing low-temperature plasma irradiation on acid water containing silicon and aluminum for cyaniding gold extraction to obtain a polyaluminum silicate precursor solution; and (4) carrying out low-temperature plasma irradiation on the polysilicate aluminum precursor solution to obtain the silicon-based flocculant. The method has the advantages of simple wastewater treatment process and wide source of required raw materials, the total cyanide content in the flocculant prepared from the cyaniding gold extraction wastewater is only 0.04mg/kg at the lowest, the prepared flocculant is applicable to a water environment with the pH value of 1-13, the heavy metal removal rate is high, the removal of 99% of lead, 98% of mercury, 98% of cadmium, 99% of zinc and 99% of copper in a simulation solution can be realized at the highest, and the method is particularly key for solving the problems existing in the current cyaniding gold extraction wastewater treatment process.
Description
Technical Field
The invention relates to a wastewater treatment method, in particular to a treatment method of cyaniding gold extraction wastewater, belonging to the field of resource utilization of hazardous wastes.
Background
Cyaniding gold extraction has the characteristics of high gold leaching rate and low equipment requirement, and is one of the most common methods for gold extraction in current gold ores. However, a large amount of toxic and harmful waste liquid is easily generated in the cyaniding gold extraction process, the treatment difficulty is high, and the serious pollution is easily caused to soil and water around a mining area. The system internal recycle is an instructive method for reducing environmental hazard caused by cyanide-containing wastewater in the gold ore mining and separation smelting process at present. In a short period, the system internal circulation can effectively avoid large-area improper discharge of cyanide gold extraction waste liquid, but the cyanide-containing waste water long-term circulation not only can easily generate a blocking effect to reduce the gold leaching rate, but also increases the dosage of a reducing agent to reduce the quality of elemental gold. Meanwhile, the circulation technology only delays the discharge of cyanide-containing waste liquid, and the harmless disposal and resource utilization of cyanide gold extraction waste liquid are not fundamentally realized. Currently, the treatment of cyanide gold extraction waste liquid mainly comprises a chemical oxidation method, a comprehensive recovery method and a regeneration method. The chemical oxidation method has the problems of large consumption of the oxidant and incomplete oxidation of cyanide. The comprehensive recovery method has the problems that a large amount of metal ions are required to be added, the treatment depth of cyanide-containing wastewater is not enough, solid waste needs to be treated secondarily and the like. The regeneration method can effectively separate metal ions and cyanides, thereby realizing the high-efficiency recovery of the cyanogens, but the method has serious corrosion to equipment, and the treated waste water has heavy metal and cyanides exceeding the standard and can not reach the emission standard.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a cyanide gold extraction wastewater treatment method which can effectively utilize heavy metal ions without adding an oxidant and the metal ions additionally.
The technical scheme is as follows: the treatment method of the cyaniding gold extraction wastewater comprises the following steps:
(1) preparing a silicon acid solution from sodium silicate and a hydrochloric acid solution;
(2) preparing aluminum-containing wastewater from aluminum chloride and gold extraction cyanide wastewater;
(3) preparing cyaniding gold-extracting silicon-aluminum-containing acidic water by using a silicon-based acid solution and cyaniding gold-extracting aluminum-containing wastewater;
(4) performing low-temperature plasma irradiation on acid water containing silicon and aluminum for cyaniding gold extraction to obtain a polyaluminum silicate precursor solution;
(5) and (4) carrying out low-temperature plasma irradiation on the polysilicate aluminum precursor solution to obtain the silicon-based flocculant.
Preferably, in the step (1), the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution is 10-30: 100 g/mL. And further, mixing the sodium silicate and the hydrochloric acid solution, and stirring until the sodium silicate is completely dissolved to obtain the silicon acid solution. Preferably, the mass fraction of the hydrochloric acid in the hydrochloric acid solution is 10-30%. If the mass fraction of the hydrochloric acid is less than 10%, the silicate is hydrolyzed, the polymerization efficiency is reduced, and the amount of the polysilicic acid colloid produced is reduced. If the mass fraction of the hydrochloric acid is higher than 30%, the hydrolysis and polymerization efficiency of the silicate is not remarkably improved, and meanwhile, the aluminum ions and cyanide pollutants adsorbed on the surface of the polysilicic acid colloid are reduced after the silicon-based acid solution and the cyanide gold-extracting aluminum-containing wastewater are mixed.
In the step (2), the solid-to-liquid ratio of the aluminum chloride to the cyaniding gold extraction wastewater is 5-15: 100 g/mL. Further, mixing and stirring the aluminum chloride and the cyaniding gold extraction wastewater until the aluminum chloride is completely dissolved to obtain the cyaniding gold extraction aluminum-containing wastewater.
In the step (3), the volume ratio of the silica-based acid solution to the aluminum-containing wastewater from cyaniding gold extraction is 0.5-1.5: 1.
In the step (4), the low-temperature plasma irradiation atmosphere is oxygen, and the voltage is 10-50 kV. And further stirring the cyaniding gold-extracting silicon-aluminum-containing acidic water while irradiating the acidic water by using low-temperature plasma, stopping stirring after 1-2 hours, and aging for 3-6 hours to obtain a polysilicon-aluminum precursor solution. If the irradiation action voltage of the low-temperature plasma is lower than 10kV, oxygen free radicals, hydroxyl free radicals, hydrogen free radicals and hydrated electrons generated by the reaction of the high-energy electron beams released by the high-voltage electrode of the low-temperature plasma with oxygen and water molecules are reduced, the high-efficiency oxidation effect dominated by the oxygen free radicals and the hydroxyl free radicals is poor in the oxygen atmosphere, the oxidation efficiency of cyanide pollutants in waste liquid is reduced, and released ions such as copper, iron, zinc, silver and gold are reduced. If the irradiation action voltage of the low-temperature plasma is higher than 50kV, the energy consumption is obviously increased, oxygen free radicals, hydroxyl free radicals, hydrogen free radicals and hydrated electrons generated by the reaction of the high-energy electron beams released by the high-voltage electrode of the low-temperature plasma and oxygen and water molecules are not obviously increased, and the oxidation efficiency of cyanide pollutants and the further promotion of released copper, iron, zinc, silver, gold and other ions are not obvious. If the aging time is less than 3 hours, the released copper, iron, zinc, silver, gold and other ions can not be effectively adsorbed on the surface of the chlorinated polysilicon aluminum colloid. If the aging time is longer than 6 hours, the ions of copper, iron, zinc, silver, gold and the like adsorbed on the surface of the chlorinated polysilicon aluminum colloid have no obvious change.
In the step (5), the low-temperature plasma irradiation atmosphere is argon, and the voltage is 10-50 kV. And further stirring the cyaniding gold-extracting silicon-aluminum-containing acidic water while irradiating the low-temperature plasma, stopping stirring after 1-2 hours, aging for 3-6 hours, drying, grinding and sieving with a 200-400-mesh sieve to obtain the silicon-based flocculant. If the low-temperature plasma irradiation action voltage is lower than 10kV, the reduction action dominated by hydrogen radicals and hydrated electrons is weakened under the argon atmosphere, and the mixed floc gel bodies of polyaluminum silicate zinc, polyaluminum ferric silicate, polyaluminum copper silicate and the like generated by the reaction of free silicate radicals in water and the hydrogen radicals and the hydrated electrons, which adsorb the ions of aluminum, copper, iron, zinc, silver, gold and the like, are reduced. If the low-temperature plasma irradiation action voltage is higher than 50kV, the reduction action dominated by hydrogen radicals and hydrated electrons is further promoted and is not obvious under the argon atmosphere, and the generation amount of mutually mixed floc gel bodies such as zinc polysilicate, iron polysilicate, copper polysilicate and the like generated by the reaction of free silicate radicals in water with the hydrogen radicals and the hydrated electrons and the like is further increased and is not obvious. If the aging time is less than 3 hours, the mutual mixing of the floc gel bodies such as the poly-silicon aluminum zinc, the poly-silicon aluminum iron, the poly-silicon aluminum copper and the like is insufficient, so that the adsorption performance of the finally generated silicon-based flocculant is deteriorated. If the aging time is longer than 6 hours, the flocculent bodies such as the poly-silicon aluminum zinc, the poly-silicon aluminum iron, the poly-silicon aluminum copper and the like are fully mixed, and the adsorption performance of the finally generated silicon-based flocculant is further not remarkably increased.
The reaction mechanism is as follows: in a strong acid environment, partial silicate is hydrolyzed and polymerized in a silicon acid solution to generate polysilicic acid colloid. After the silica-based acid solution and the cyaniding gold-extracting aluminum-containing wastewater are mixed, aluminum ions and cyaniding pollutants are adsorbed on the surface of the polysilicic acid colloid. Under the irradiation of low-temperature plasma, high-energy electron beams released by the high-voltage electrode of the low-temperature plasma react with oxygen and water molecules to generate oxygen radicals, hydroxyl radicals, hydrogen radicals and hydrated electrons. Under the oxygen atmosphere, the high-efficiency oxidation effect dominated by oxygen radicals and hydroxyl radicals is more remarkable. The oxygen free radical and the hydroxyl free radical react with cyanide pollutants in the waste liquid, including single cyanide, thiocyanate ions, cuprous cyanide complex ions, zinc cyanide complex ions, iron cyanide complex ions and gold cyanide complex ions to generate carbonate, nitrate, sulfate and water, and ions such as copper, iron, zinc, silver, gold and the like are released. Meanwhile, chloride ions can enhance the oxidation process of cyanide pollutants through a chloride ion-chlorine-hypochlorous acid-chloride ion conversion path. The released copper, iron, zinc, silver, gold and other ions are adsorbed on the surface of the polysilicic acid colloid. In an oxygen atmosphere, the hydrogen radical and hydrated electron dominated reduction is more pronounced. The polysilicone gel absorbing the ions of aluminum, copper, iron, zinc, silver, gold, etc. and the free silicate in water react with hydrogen radical and hydrated electron to produce mixed floc gel of polysilicone aluminum zinc, polysilicone aluminum iron, polysilicone aluminum copper, etc.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the method has the advantages of simple wastewater treatment process and wide source of required raw materials, the total cyanide content in the flocculant prepared from the cyaniding gold extraction wastewater is only 0.04mg/kg at the lowest, the prepared flocculant is applicable to a water environment with the pH value of 1-13, the heavy metal removal rate is high, the removal of 99% of lead, 98% of mercury, 98% of cadmium, 99% of zinc and 99% of copper in a simulation solution can be realized at the highest, and the method is particularly key for solving the problems existing in the current cyaniding gold extraction wastewater treatment process.
Drawings
FIG. 1 is a flow chart of the wastewater treatment process of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The cyaniding gold extraction wastewater used by the invention is taken from large water clear gold mine of inner Mongolia, and the waste liquid contains 102mg/L of single cyanide, 89mg/L of thiocyanide ions, 213mg/L of cuprous cyanide complex ions, 265mg/L of zinc cyanide complex ions, 73mg/L of iron cyanide complex ions and 24mg/L of gold cyanide complex ions.
Example 1 solid-liquid ratio of sodium silicate and hydrochloric acid solutions impact on the Performance of the flocculant prepared
Respectively weighing sodium silicate and hydrochloric acid solution according to the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution of 5:100g/mL, 7:100g/mL, 9:100g/mL, 10:100g/mL, 20:100g/mL, 30:100g/mL, 32:100g/mL, 35g/mL and 40:100g/mL, mixing, and stirring until the sodium silicate is completely dissolved to obtain the silicon-based acid solution, wherein the mass fraction of the hydrochloric acid in the hydrochloric acid solution is 10%. Respectively weighing the aluminum chloride and the cyaniding gold extraction wastewater according to the solid-liquid ratio of the aluminum chloride to the cyaniding gold extraction wastewater of 5:100g/mL, mixing, and stirring until the aluminum chloride is completely dissolved to obtain the cyaniding gold extraction aluminum-containing wastewater. Respectively measuring the silicon-based acid solution and the cyaniding gold-extracting aluminum-containing wastewater according to the volume ratio of the silicon-based acid solution to the cyaniding gold-extracting aluminum-containing wastewater of 0.5:1, mixing, and uniformly stirring to obtain the cyaniding gold-extracting aluminum-containing acidic water. Stirring the cyaniding gold-extracting silicon-aluminum-containing acidic water at the rotating speed of 120rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 1 hour, and aging for 3 hours to obtain a polysilicon-aluminum precursor solution, wherein the low-temperature plasma irradiation action voltage is 10kV, and the irradiation atmosphere is oxygen. Stirring the polysilicate aluminum precursor solution at the rotating speed of 120rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 1 hour, aging for 3 hours, drying, grinding and sieving by a 200-mesh sieve to obtain the silicon-based flocculant, wherein the low-temperature plasma irradiation action voltage is 10kV, and the irradiation atmosphere is argon.
Determination of total cyanide: the total cyanide content of the flocculant prepared by the invention is determined according to spectrophotometry for determining soil cyanide and total cyanide (HJ 745-2015).
Treating the water body containing heavy metal pollutants: according to the solid-liquid ratio of the prepared flocculant to the water body containing the heavy metal pollutants of 5:1(g/L), the flocculant adsorbent is put into the water body containing the heavy metal pollutants of which the initial pH is 1 and which contains 10mg/L cadmium, 10mg/L lead, 1mg/L mercury, 100mg/L zinc and 100mg/L copper, and is stirred for 30min at the rotating speed of 120 rpm.
Detecting the concentration of the heavy metal ions and calculating the removal rate: wherein the concentration of four pollutants of zinc, copper, lead and cadmium in the water body is measured according to the inductively coupled plasma emission spectrometry for measuring 32 elements in water (HJ 776-2015); the concentration of mercury pollutants in the water body is according to the water quality mercury,Determination of arsenic, selenium, bismuth and antimony by atomic fluorescence assay (HJ 694-2014). The removal rate of heavy metal M (M: cadmium, lead, mercury, zinc and copper) is calculated according to the following formula, wherein RMRemoval rate of heavy metal contaminants, cM0The initial concentration (mg/L) of heavy metal M in the water body, cMtThe concentration (mg/L) of heavy metal M in the water body after the treatment of the adsorbent. The test results are shown in Table 1.
TABLE 1 influence of solid-liquid ratio of sodium silicate and hydrochloric acid solutions on the performance of the prepared flocculants
As can be seen from table 1, when the solid-to-liquid ratio of the sodium silicate and the hydrochloric acid solution is less than 10:100g/mL (as in table 1, when the solid-to-liquid ratio of the sodium silicate and the hydrochloric acid solution is 9:100g/mL, 7:100g/mL, 5:100g/mL and lower values not listed in table 1), the amount of the sodium silicate is less, the amount of the polysilicic acid colloid generated is less, aluminum ions and cyanide pollutants adsorbed on the surface of the polysilicic acid colloid are reduced, so that the finally generated mutually mixed floc gel of the zinc polysilicate, the iron polysilicate, the copper aluminum and the like is reduced, the total cyanide in the flocculant is remarkably increased as the solid-to-liquid ratio of the sodium silicate and the hydrochloric acid solution is reduced, and the heavy metal removal rate is remarkably reduced as the solid-to-liquid ratio of the sodium silicate and the hydrochloric acid solution is reduced. When the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution is 10-30: 100g/mL (as shown in table 1, the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution is 10:100g/mL, 20:100g/mL, or 30:100g/mL), in a strong acid environment, partial silicate is hydrolyzed and polymerized in the silicon acid solution to generate polysilicic acid colloid. After the silica-based acid solution and the cyaniding gold-extracting aluminum-containing wastewater are mixed, aluminum ions and cyaniding pollutants are adsorbed on the surface of the polysilicic acid colloid. The colloid of silicon aluminium chloride adsorbing aluminium, copper, iron, zinc, silver and gold ions and the free silicate in water react with hydrogen radical and hydrated electron to produce flocculated gel of zinc polysilicate, iron polysilicate and copper polysilicate. Finally, the total cyanide content of the generated flocculating agent is lower than 0.4mg/kg, and the heavy metal removal rate is higher than 90%. When the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution is greater than 30:100g/mL (as shown in Table 1, when the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution is 32:100g/mL, 35:100g/mL, 40:100g/mL and higher values not listed in Table 1), the sodium silicate is excessive, the silicate is hydrolyzed, the polymerization efficiency is reduced, the generated polysilicic acid colloid is reduced, the total cyanide in the flocculant is obviously increased along with the further increase of the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution, and the removal rate of heavy metals is obviously reduced along with the further increase of the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution. Therefore, in summary, the benefit and the cost are combined, and when the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution is equal to 10-30: 100g/mL, the performance of the prepared flocculant is most favorably improved.
Example 2 Effect of solid-liquid ratio of aluminum chloride to cyaniding gold extraction wastewater on the Performance of the prepared flocculant
Respectively weighing sodium silicate and hydrochloric acid solution according to the solid-to-liquid ratio of 30:100g/mL of the sodium silicate and the hydrochloric acid solution, mixing, and stirring until the sodium silicate is completely dissolved to obtain the silicon-based acid solution, wherein the mass fraction of the hydrochloric acid in the hydrochloric acid solution is 20%. Respectively weighing the aluminum chloride and the gold cyanide extraction wastewater according to the solid-liquid ratio of the aluminum chloride to the gold cyanide extraction wastewater of 2.5:100g/mL, 3.5:100g/mL, 4.5:100g/mL, 5:100g/mL, 10:100g/mL, 15:100g/mL, 15.5:100g/mL, 16.5:100g/mL and 17.5:100g/mL, mixing, and stirring until the aluminum chloride is completely dissolved to obtain the aluminum-containing wastewater of the gold cyanide extraction. Respectively measuring the silicon-based acid solution and the cyaniding gold-extracting aluminum-containing wastewater according to the volume ratio of the silicon-based acid solution to the cyaniding gold-extracting aluminum-containing wastewater of 1:1, mixing and uniformly stirring to obtain the cyaniding gold-extracting aluminum-containing acidic water. Stirring the cyaniding gold-extraction silicon-aluminum-containing acidic water at the rotating speed of 300rpm, simultaneously carrying out low-temperature plasma irradiation, stopping stirring after 1.5 hours, and aging for 4.5 hours to obtain a polysilicate aluminum precursor solution, wherein the low-temperature plasma irradiation action voltage is 30kV, and the irradiation atmosphere is oxygen. Stirring the polysilicon aluminum precursor solution at the rotating speed of 300rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 1.5 hours, aging for 4.5 hours, drying, grinding and sieving with a 300-mesh sieve to obtain the silicon-based flocculant, wherein the low-temperature plasma irradiation action voltage is 30kV, and the irradiation atmosphere is argon.
The determination of total cyanide, the treatment of the water containing heavy metal pollutants, the detection of the concentration of heavy metal ions and the calculation of the removal rate are the same as those in example 1. The test results are shown in Table 2.
TABLE 2 solid-liquid ratio of aluminum chloride to cyaniding gold extraction wastewater on the performance of the prepared flocculant
As can be seen from table 2, when the solid-liquid ratio of the aluminum chloride to the gold extraction cyanide wastewater is less than 5:100g/mL (as shown in table 2, when the solid-liquid ratio of the aluminum chloride to the gold extraction cyanide wastewater is 4.5:100g/mL, 3.5:100g/mL, 2.5:100g/mL and lower values not listed in table 2), less aluminum chloride is generated, and aluminum ions adsorbed on the surface of polysilicic acid colloid are reduced after mixing the silica-based acid solution and the gold extraction cyanide aluminum-containing wastewater, so that finally generated floc gel bodies such as zinc polysilicate, iron polysilicate, copper polysilicate and the like are reduced, resulting in a significant increase of the total cyanide in the flocculant along with the decrease of the solid-liquid ratio of the aluminum chloride to the gold extraction cyanide wastewater and a significant decrease of the removal rate of heavy metals along with the decrease of the solid-liquid ratio of the aluminum chloride to the gold extraction cyanide wastewater. When the solid-liquid ratio of the aluminum chloride to the gold cyanide extraction wastewater is 5-15: 100g/mL (as shown in Table 2, the solid-liquid ratio of the aluminum chloride to the gold cyanide extraction wastewater is 5:100g/mL, 10:100g/mL, 15:100g/mL), and a proper amount of aluminum chloride, aluminum ions and cyanide pollutants are adsorbed on the surface of the polysilicone colloid after the silica-based acid solution and the gold cyanide extraction aluminum-containing wastewater are mixed. The colloid of silicon aluminium chloride adsorbing aluminium, copper, iron, zinc, silver and gold ions and the free silicate in water react with hydrogen radical and hydrated electron to produce flocculated gel of zinc polysilicate, iron polysilicate and copper polysilicate. Finally, the total cyanide content of the generated flocculating agent is lower than 0.25mg/kg, and the heavy metal removal rate is higher than 93%. When the solid-liquid ratio of the aluminum chloride to the gold extraction cyanide wastewater is greater than 15:100g/mL (as shown in table 2, when the solid-liquid ratio of the aluminum chloride to the gold extraction cyanide wastewater is 15.5:100g/mL, 16.5:100g/mL, 17.5:100g/mL and higher values not listed in table 2), the aluminum chloride is excessive, and aluminum ions and ions such as copper, iron, zinc, silver, gold compete for active sites on the surface of the aluminum polysilicate aluminum chloride colloid, so that the finally generated gel flocs of zinc polysilicate aluminum, iron polysilicate aluminum, copper aluminum and the like are reduced, the total cyanide in the flocculant is remarkably increased along with further increase of the solid-liquid ratio of the aluminum chloride to the gold extraction cyanide wastewater, and the removal rate of heavy metals is remarkably reduced along with further increase of the solid-liquid ratio of the aluminum chloride to the gold extraction cyanide wastewater. Therefore, in summary, the benefit and the cost are combined, and when the solid-liquid ratio of the aluminum chloride to the cyaniding gold extraction wastewater is 5-15: 100g/mL, the performance of the prepared flocculant is most favorably improved.
Example 3 volume ratio of silica-based acid solution and cyaniding gold extraction aluminum-containing wastewater
Respectively weighing sodium silicate and hydrochloric acid solution according to the solid-to-liquid ratio of 30:100g/mL of the sodium silicate and the hydrochloric acid solution, mixing, and stirring until the sodium silicate is completely dissolved to obtain the silicon-based acid solution, wherein the mass fraction of hydrochloric acid in the hydrochloric acid solution is 30%. Respectively weighing the aluminum chloride and the cyaniding gold extraction wastewater according to the solid-liquid ratio of the aluminum chloride to the cyaniding gold extraction wastewater of 15:100g/mL, mixing, and stirring until the aluminum chloride is completely dissolved to obtain the cyaniding gold extraction aluminum-containing wastewater. Respectively weighing the silica-based acid solution and the cyaniding gold-extracting aluminum-containing wastewater according to the volume ratio of the silica-based acid solution to the cyaniding gold-extracting aluminum-containing wastewater of 0.25:1, 0.35:1, 0.45:1, 0.5:1, 1:1, 1.5:1, 1.55:1, 1.65:1 and 1.75:1, mixing and uniformly stirring to obtain the cyaniding gold-extracting aluminum-containing acidic water. Stirring the cyaniding gold-extracting silicon-aluminum-containing acidic water at 480rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 2 hours, and aging for 6 hours to obtain a polysilicon aluminum precursor solution, wherein the low-temperature plasma irradiation action voltage is 50kV, and the irradiation atmosphere is oxygen. Stirring the polysilicate aluminum precursor solution at 480rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 2 hours, aging for 6 hours, drying, grinding and sieving with a 400-mesh sieve to obtain the silicon-based flocculant, wherein the low-temperature plasma irradiation action voltage is 50kV, and the irradiation atmosphere is argon.
The determination of total cyanide, the treatment of the water containing heavy metal pollutants, the detection of the concentration of heavy metal ions and the calculation of the removal rate are the same as those in example 1. The test results are shown in Table 3.
TABLE 3 volume ratio of silica-based acid solution to cyaniding gold extraction aluminum-containing wastewater to influence on performance of flocculant prepared
As can be seen from table 3, when the volume ratio of the silica-based solution to the aluminum-containing wastewater from cyaniding gold extraction is less than 0.5:1 (as shown in table 3, when the volume ratio of the silica-based solution to the aluminum-containing wastewater from cyaniding gold extraction is 0.45:1, 0.35:1, 0.25:1 and lower ratios not listed in table 3), the amount of sodium silicate and hydrochloric acid is less, so that the amount of polysilicic acid colloid generated is reduced, the total cyanides in the flocculant are increased significantly as the volume ratio of the silica-based solution to the aluminum-containing wastewater from cyaniding gold extraction is reduced, and the heavy metal removal rate is decreased significantly as the volume ratio of the silica-based solution to the aluminum-containing wastewater from cyaniding gold extraction is reduced. When the volume ratio of the silicon-based acid solution to the aluminum-containing waste water from the cyaniding gold extraction is 0.5-1.5: 1 (as shown in table 3, the volume ratio of the silicon-based acid solution to the aluminum-containing waste water from the cyaniding gold extraction is 0.5:1, 1:1, 1.5:1), the oxygen radicals and the hydroxyl radicals react with cyaniding pollutants in the waste liquid, including mono-cyanide, thiocyanate ions, cuprous cyanide complex ions, zinc cyanide complex ions, iron cyanide complex ions, and gold cyanide complex ions, to generate carbonate, nitrate, sulfate and water, and ions such as copper, iron, zinc, silver, gold and the like are released. Meanwhile, chloride ions can enhance the oxidation process of cyanide pollutants through a chloride ion-chlorine-hypochlorous acid-chloride ion conversion way and promote the reaction of aluminum and polysilicic acid colloid to generate chlorinated poly-silicon-aluminum colloid. The released copper, iron, zinc, silver, gold and other ions are adsorbed on the surface of the chlorinated poly-silicon aluminum colloid. The colloid of silicon aluminium chloride adsorbing aluminium, copper, iron, zinc, silver and gold ions and the free silicate in water react with hydrogen radical and hydrated electron to produce flocculated gel of zinc polysilicate, iron polysilicate and copper polysilicate. Finally, the total cyanide content of the generated flocculating agent is lower than 0.15mg/kg, and the heavy metal removal rate is higher than 96%. When the volume ratio of the silica-based acid solution to the aluminum-containing waste water from the cyaniding gold extraction is more than 1.5:1 (as shown in table 3, when the volume ratio of the silica-based acid solution to the aluminum-containing waste water from the cyaniding gold extraction is 1.55:1, 1.65:1, 1.75:1 and higher ratios not listed in table 3), the sodium silicate and the hydrochloric acid are both excessive, ions of copper, iron, zinc, silver, gold and the like released from cyaniding pollutants are reduced, so that the finally generated mixed gel flocs of poly-aluminum-zinc-silicon-aluminum-zinc, poly-aluminum-iron, poly-aluminum-copper and the like are reduced, the total cyanides in the flocculant are obviously increased along with the further increase of the volume ratio of the silica-based acid solution to the aluminum-containing waste water from the cyaniding gold extraction, and the removal rate of heavy metals is obviously reduced along with the further increase of the volume ratio of the silica-based acid solution to the aluminum-containing waste water from the cyaniding gold extraction. Therefore, in summary, the benefits and the cost are combined, and when the volume ratio of the silica-based acid solution to the cyaniding gold-extracting aluminum-containing wastewater is 0.5-1.5: 1, the performance of the prepared flocculant is most favorably improved.
Comparative example 1 comparison of the performances of the flocculant prepared by using the cyaniding gold extraction wastewater of the invention and the comparative flocculant
The preparation of the flocculant of the invention comprises the following steps: respectively weighing sodium silicate and hydrochloric acid solution according to the solid-to-liquid ratio of 30:100g/mL of the sodium silicate and the hydrochloric acid solution, mixing, and stirring until the sodium silicate is completely dissolved to obtain the silicon-based acid solution, wherein the mass fraction of hydrochloric acid in the hydrochloric acid solution is 30%. Respectively weighing the aluminum chloride and the cyaniding gold extraction wastewater according to the solid-liquid ratio of the aluminum chloride to the cyaniding gold extraction wastewater of 15:100g/mL, mixing, and stirring until the aluminum chloride is completely dissolved to obtain the cyaniding gold extraction aluminum-containing wastewater. Respectively measuring the silicon-based acid solution and the cyaniding gold-extracting aluminum-containing wastewater according to the volume ratio of the silicon-based acid solution to the cyaniding gold-extracting aluminum-containing wastewater of 1.5:1, mixing, and uniformly stirring to obtain the cyaniding gold-extracting aluminum-containing acidic water. Stirring the cyaniding gold-extracting silicon-aluminum-containing acidic water at 480rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 2 hours, and aging for 6 hours to obtain a polysilicon aluminum precursor solution, wherein the low-temperature plasma irradiation action voltage is 50kV, and the irradiation atmosphere is oxygen. Stirring the polysilicate aluminum precursor solution at 480rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 2 hours, aging for 6 hours, drying, grinding and sieving with a 400-mesh sieve to obtain the silicon-based flocculant, wherein the low-temperature plasma irradiation action voltage is 50kV, and the irradiation atmosphere is argon.
Preparation of comparative flocculant 1: respectively weighing the aluminum chloride and the cyaniding gold extraction wastewater according to the solid-liquid ratio of the aluminum chloride to the cyaniding gold extraction wastewater of 15:100g/mL, mixing, and stirring until the aluminum chloride is completely dissolved to obtain the cyaniding gold extraction aluminum-containing wastewater. Stirring the aluminum-containing wastewater from the cyaniding gold extraction at 480rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 2 hours, and aging for 6 hours to obtain a precursor solution, wherein the low-temperature plasma irradiation action voltage is 50kV, and the irradiation atmosphere is oxygen. Stirring the precursor solution at 480rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 2 hours, aging for 6 hours, drying, grinding and sieving with a 400-mesh sieve to obtain the comparative flocculant 1, wherein the low-temperature plasma irradiation action voltage is 50kV, and the irradiation atmosphere is argon.
Preparation of comparative flocculant 2: respectively weighing sodium silicate and hydrochloric acid solution according to the solid-to-liquid ratio of 30:100g/mL of the sodium silicate and the hydrochloric acid solution, mixing, and stirring until the sodium silicate is completely dissolved to obtain the silicon-based acid solution, wherein the mass fraction of hydrochloric acid in the hydrochloric acid solution is 30%. Respectively measuring the silicon-based acid solution and the cyaniding gold extraction wastewater according to the volume ratio of the silicon-based acid solution to the cyaniding gold extraction wastewater of 1.5:1, mixing and uniformly stirring to obtain the cyaniding gold extraction silicon-containing acidic water. Stirring the silicon-containing acidic water for cyaniding gold extraction at 480rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 2 hours, and aging for 6 hours to obtain a polysilicon precursor solution, wherein the low-temperature plasma irradiation action voltage is 50kV, and the irradiation atmosphere is oxygen. Stirring the polysilicon precursor solution at 480rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 2 hours, aging for 6 hours, drying, grinding and sieving with a 400-mesh sieve to obtain a comparative flocculant 2, wherein the low-temperature plasma irradiation action voltage is 50kV, and the irradiation atmosphere is argon.
Preparation of comparative flocculant 3: respectively weighing sodium silicate and hydrochloric acid solution according to the solid-to-liquid ratio of 30:100g/mL of the sodium silicate and the hydrochloric acid solution, mixing, and stirring until the sodium silicate is completely dissolved to obtain the silicon-based acid solution, wherein the mass fraction of hydrochloric acid in the hydrochloric acid solution is 30%. Respectively weighing the aluminum chloride and the cyaniding gold extraction wastewater according to the solid-liquid ratio of the aluminum chloride to the cyaniding gold extraction wastewater of 15:100g/mL, mixing, and stirring until the aluminum chloride is completely dissolved to obtain the cyaniding gold extraction aluminum-containing wastewater. Respectively measuring the silicon-based acid solution and the cyaniding gold-extracting aluminum-containing wastewater according to the volume ratio of the silicon-based acid solution to the cyaniding gold-extracting aluminum-containing wastewater of 1.5:1, mixing, and uniformly stirring to obtain the cyaniding gold-extracting aluminum-containing acidic water. Stirring the cyaniding gold-extraction silicon-aluminum-containing acidic water at 480rpm, simultaneously performing low-temperature plasma irradiation, stopping stirring after 2 hours, aging for 6 hours, drying, grinding and sieving with a 400-mesh sieve to obtain a contrast flocculant 2, wherein the low-temperature plasma irradiation action voltage is 50kV, and the irradiation atmosphere is oxygen.
Preparation of comparative flocculant 4: respectively weighing sodium silicate and hydrochloric acid solution according to the solid-to-liquid ratio of 30:100g/mL of the sodium silicate and the hydrochloric acid solution, mixing, and stirring until the sodium silicate is completely dissolved to obtain the silicon-based acid solution, wherein the mass fraction of hydrochloric acid in the hydrochloric acid solution is 30%. Respectively weighing the aluminum chloride and the cyaniding gold extraction wastewater according to the solid-liquid ratio of the aluminum chloride to the cyaniding gold extraction wastewater of 15:100g/mL, mixing, and stirring until the aluminum chloride is completely dissolved to obtain the cyaniding gold extraction aluminum-containing wastewater. Respectively measuring the silica-based solution and the cyaniding gold-extraction aluminum-containing wastewater according to the volume ratio of the silica-based solution to the cyaniding gold-extraction aluminum-containing wastewater of 1.5:1, mixing, uniformly stirring, aging for 6 hours, drying, grinding and sieving by a 400-mesh sieve to obtain a comparative flocculant 3.
The determination of total cyanide, the treatment of the water containing heavy metal pollutants, the detection of the concentration of heavy metal ions and the calculation of the removal rate are the same as those in example 1. The test results are shown in Table 4.
TABLE 4 comparison of the Performance of flocculants prepared by using cyanide gold extraction wastewater of the present invention and comparative flocculants
As can be seen from Table 4, the total cyanide content of the flocculants of the invention was much lower than that of comparative flocculant 1, comparative flocculant 2, comparative flocculant 3, comparative flocculant 4; the heavy metal removal rate of the flocculant is far higher than that of a contrast flocculant 1, a contrast flocculant 2, a contrast flocculant 3 and a contrast flocculant 4. For any heavy metal pollutant, the removal rate of the flocculant is higher than the sum of the removal rates of the comparative flocculant 1, the comparative flocculant 2, the comparative flocculant 3 and the comparative flocculant 4. Therefore, it can be concluded from the results in table 4 that, in the oxygen atmosphere, the oxygen radicals and the hydroxyl radicals not only can oxidize and degrade cyanide pollutants in the waste liquid and release copper, iron, zinc, silver, gold and other ions, but also can realize the catalytic conversion of chlorine in the waste liquid so as to promote the reaction of aluminum ions and polysilicic acid colloid and generate the chlorinated poly-silicon-aluminum colloid. Under an argon atmosphere, the hydrogen radical and hydrated electron dominated reduction is more pronounced. The colloid of silicon aluminium chloride adsorbing aluminium, copper, iron, zinc, silver and gold ions and the free silicate in water react with hydrogen radical and hydrated electron to produce flocculated gel of zinc polysilicate, iron polysilicate and copper polysilicate.
Claims (10)
1. A treatment method of cyaniding gold extraction wastewater is characterized by comprising the following steps:
(1) preparing a silicon acid solution from sodium silicate and a hydrochloric acid solution;
(2) preparing aluminum-containing wastewater from aluminum chloride and gold extraction cyanide wastewater;
(3) preparing cyaniding gold-extracting silicon-aluminum-containing acidic water by using a silicon-based acid solution and cyaniding gold-extracting aluminum-containing wastewater;
(4) performing low-temperature plasma irradiation on acid water containing silicon and aluminum for cyaniding gold extraction to obtain a polyaluminum silicate precursor solution;
(5) and (4) carrying out low-temperature plasma irradiation on the polysilicate aluminum precursor solution to obtain the silicon-based flocculant.
2. The method for treating cyanide gold-extracting wastewater according to claim 1, which is characterized in that: in the step (1), the solid-to-liquid ratio of the sodium silicate to the hydrochloric acid solution is 10-30: 100 g/mL.
3. The method for treating cyanide gold-extracting wastewater according to claim 1, which is characterized in that: in the step (2), the solid-to-liquid ratio of the aluminum chloride to the cyaniding gold extraction wastewater is 5-15: 100 g/mL.
4. The method for treating cyanide gold-extracting wastewater according to claim 1, which is characterized in that: in the step (3), the volume ratio of the silica-based acid solution to the aluminum-containing wastewater from cyaniding gold extraction is 0.5-1.5: 1.
5. The method for treating cyanide gold-extracting wastewater according to claim 1, which is characterized in that: in the step (4), the low-temperature plasma irradiation atmosphere is oxygen, and the voltage is 10-50 kV.
6. The method for treating cyanide gold-extracting wastewater according to claim 1, which is characterized in that: in the step (5), the low-temperature plasma irradiation atmosphere is argon, and the voltage is 10-50 kV.
7. The method for treating cyanide gold-extracting wastewater according to claim 1, which is characterized in that: and (4) stirring the cyaniding gold-extracting silicon-aluminum-containing acidic water while irradiating the acidic water by using low-temperature plasma, stopping stirring after 1-2 hours, and aging for 3-6 hours to obtain a polysilicon aluminum precursor solution.
8. The method for treating cyanide gold-extracting wastewater according to claim 1, which is characterized in that: and (5) stirring the cyaniding gold-extracting silicon-aluminum-containing acidic water while irradiating the acidic water by using low-temperature plasma, stopping stirring after 1-2 hours, aging for 3-6 hours, drying, grinding and sieving by using a 200-400-mesh sieve to obtain the silicon-based flocculant.
9. The method for treating cyanide gold-extracting wastewater according to claim 1, which is characterized in that: in the step (2), the aluminum chloride and the cyaniding gold extraction wastewater are mixed and stirred until the aluminum chloride is completely dissolved, so as to obtain the cyaniding gold extraction aluminum-containing wastewater.
10. The method for treating cyanide gold-extracting wastewater according to claim 1, which is characterized in that: in the step (1), the mass fraction of hydrochloric acid in the hydrochloric acid solution is 10-30%.
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