CN107569811B - Method for efficiently removing mercury from mercury-containing hazardous waste residue by using full-wet method - Google Patents
Method for efficiently removing mercury from mercury-containing hazardous waste residue by using full-wet method Download PDFInfo
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Abstract
The invention discloses a method for efficiently removing mercury from mercury-containing dangerous waste residues by a full-wet method, which comprises the steps of oxidizing the mercury-containing dangerous waste residues by using an acidic persulfate solution, adjusting the pH value of the mercury-containing dangerous waste residues to be more than 7, sequentially leaching by using a thiosulfate solution, leaching by using a mixed solution of organic acid and iodide, and leaching by using a mixed solution of sodium sulfide and sodium hydroxide.
Description
Technical Field
The invention relates to a method for treating mercury-containing dangerous waste residues, in particular to a method for treating mercury-containing dangerous waste residues through chemical leaching, and belongs to the technical field of waste treatment.
Background
In recent years, with the rapid development of industry and agriculture, mercury is discharged in large quantities during production and use, and the national waste records list mercury-containing waste as HW29 waste. The dangerous waste residue containing mercury mainly refers to solid waste containing mercury generated in the industries of mercury ore mining and smelting, chlor-alkali industry, battery and thermometer production and the like. The mercury-containing waste has high mercury content, and if the waste is not properly treated, the mercury and compounds in the soil can enter human bodies through food chains, so that the mercury and the compounds in the soil can pollute the atmosphere, the surrounding soil, surface water and underground water, and the mercury and the compounds in the soil can cause great harm to the human bodies. Therefore, the method selects a proper method to safely dispose the mercury-containing hazardous waste residues, and has important significance for environmental management and human health protection in China.
Mercury can be divided into, according to chemical form: metallic mercury, inorganic combined mercury and organic combined mercury. Inorganic stateMainly in free form of Hg2+And Hg+In the form of Hg+Can form insoluble mercury salt, Hg2+Mostly soluble mercury salts. The mercury in the organic compound state is mainly short-chain alkyl mercury, the mercury is covalently matched with other small molecules or biological macromolecules, and the state formed by the covalent coordination or the supermolecular combination of the mercury and a ligand is a combined state, and the organic mercury compound is sensitive to light and heat and has higher volatility.
The present invention relates to a method for treating mercury-containing waste, and is characterized by that it utilizes chemical leaching method to make detoxication treatment of mercury-containing dangerous waste residue to reduce mercury content in the waste residue and leach out toxicity, and can make it become general waste with less harm, then according to the actual condition it can utilize resource or can be fed into general industrial solid waste landfill to make landfill, compared with conventional method it can greatly reduce treatment cost of mercury-containing waste. However, the leaching efficiency of the general leaching agent is not high, and the leaching waste liquid is easy to cause secondary pollution. The key point of the method is to find an efficient and environment-friendly leaching agent.
At present, relative reports on leaching of dangerous waste residues containing mercury are very few, and only a small amount of reports can be found on related methods such as leaching and extraction in the aspect of mercury-polluted soil, Chinese patent (CN106433649A) discloses an eluent combination consisting of an agent A consisting of hydrochloric acid, potassium iodide and a sodium thiosulfate solution and an agent B consisting of a sodium hydroxide solution and a sodium hypochlorite solution. Chinese patent (CN101362145A) discloses the use of Na2A method for simultaneously removing cadmium, copper, lead, zinc, arsenic, mercury and other heavy metals in soil by combining EDTA, oxalic acid and potassium iodide and leaching in stepsThe potassium iodide has higher removal rate of mercury in the soil, and the removal rate reaches 40.1%. The methods can remove part of mercury in the mercury-contaminated soil to a certain extent, but the mercury-containing dangerous waste residues are mercury-enriched residues, the mercury content is high, the forms of mercury are diversified, and the general method for removing mercury-contaminated soil is difficult to adapt to the mercury removal treatment of the mercury-containing dangerous waste residues.
Disclosure of Invention
Aiming at the defects of the method for treating the dangerous waste residue containing mercury in the prior art, the invention aims to provide the method for treating the dangerous waste residue containing mercury, which can realize the high-efficiency removal of multiple valence states of mercury in the dangerous waste residue containing mercury, change the dangerous waste residue containing mercury into common waste and has low secondary pollution degree to the environment.
In order to realize the aim of the invention, the invention provides a method for efficiently removing mercury from mercury-containing hazardous waste residue by a full-wet method, which comprises the following steps:
1) crushing, grinding and sieving the mercury-containing hazardous waste residue, and taking fine mercury-containing hazardous waste residue particles under the sieve;
2) adding water into the mercury-containing hazardous waste residue fine particles for moisture preservation, adding an oxidant solution, stirring and heating for oxidation treatment;
3) adjusting the pH value of the mercury-containing hazardous waste residue fine particles after oxidation treatment to be more than 7;
4) adding thiosulfate solution for leaching, and then adding water for cleaning;
5) adding a mixed solution of organic acid and iodized salt for leaching, and then adding water for cleaning;
6) adding mixed solution of sodium sulfide and sodium hydroxide for leaching, and then adding water for cleaning.
In a preferred embodiment, the oxidant solution is a persulfate solution. In a more preferable scheme, the mass percentage concentration of the persulfate solution is 0.1-1%. It is within the understanding of one skilled in the art that the persulfate solutions of the present invention include an appropriate amount of acid as a catalyst to increase the efficiency of oxidation. Such as mixing 4% to the leftThe persulfate solution was added to a 5% HCl solution in a volume ratio of 1: 10. In order to ensure that low-valent mercury such as organic mercury, monovalent mercury and the like in the mercury-containing hazardous waste residue can be completely converted into Hg2+The effective components in the persulfate are slightly excessive relative to the mercury element in the dangerous waste residue containing mercury.
In a preferable scheme, the molar ratio of the persulfate to the mercury element in the mercury-containing hazardous waste residue is not less than 2: 1. In a more preferred embodiment, the persulfate salt comprises potassium persulfate and/or sodium persulfate. More preferably potassium persulfate.
In a preferable scheme, the concentration of the thiosulfate solution is 0.01-0.3 mol/L. In a more preferred embodiment, the thiosulfate includes at least one of sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, calcium thiosulfate and magnesium thiosulfate. More preferably sodium thiosulfate.
Preferably, the concentration of the organic acid in the mixed solution of the organic acid and the iodized salt is 0.5-1 mol/L, and the concentration of the iodized salt is 0.01-0.3 mol/L;
in a more preferable scheme, the organic acid comprises at least one of citric acid, tartaric acid and oxalic acid; more preferably citric acid.
In a more preferred embodiment, the iodine salt includes at least one of potassium iodide, sodium iodide, magnesium iodide, and ammonium iodide. More preferably potassium iodide.
In the preferable scheme, the mass percentage concentration of sodium sulfide in the mixed solution of sodium sulfide and sodium hydroxide is 5-10%, and the mass of sodium hydroxide is 1-2% of the mass of sodium sulfide.
In the preferable scheme, in the leaching process of the thiosulfate solution in the step 4), the liquid-solid ratio is 5: 1-10: 1mL/g, and the leaching time is 3-12 h.
In a preferable scheme, in the leaching process of the mixed solution of the organic acid and the iodized salt in the step 5), the liquid-solid ratio is 5: 1-10: 1mL/g, and the leaching time is 3-12 h.
In the preferable scheme, in the leaching process of the mixed solution of sodium sulfide and sodium hydroxide in the step 6), the liquid-solid ratio is 2: 1-5: 1mL/g, and the leaching time is 3-12 h.
The technical scheme of the invention adopts alkaline substances to adjust the pH value of the mercury-containing hazardous waste residue fine particles after oxidation treatment to be more than 7, wherein the alkaline substances comprise at least one of calcium oxide, calcium hydroxide, calcium carbonate, sodium hydroxide, potassium hydroxide and ammonia water. The pH value of the mercury-containing hazardous waste residue fine particles is preferably adjusted to 7-8, and the subsequent leaching of thiosulfate is facilitated under neutral and alkalescent conditions.
The leaching method is mainly provided aiming at the treatment of the mercury-containing dangerous waste residue, the mercury-containing dangerous waste residue contains mercury in various valence states, for example, zero-valent mercury, monovalent mercury and divalent mercury can exist at the same time under the common condition, and the mercury in the valence states has great harm to the environment and human bodies. A large number of studies have shown that Hg2+The compound with high solubility is more easily formed by the complexation of thiosulfate ions, iodide ions and the like in the leaching solution and is leached out. The invention can convert all mercury in the dangerous waste residue containing mercury into a divalent mercury form to enter the leaching solution for leaching through modes of oxidation, complexation and the like.
According to the technical scheme, the mercury-containing hazardous waste residue is subjected to oxidation treatment in advance, zero-valent mercury, organic mercury, monovalent mercury and the like in the mercury-containing hazardous waste residue are fully oxidized into divalent mercury, and the divalent mercury is more easily complexed into a soluble compound to enter the leachate.
According to the technical scheme, after oxidation treatment, an alkaline material or an alkaline solution is added to adjust the pH of the waste residue to be neutral or slightly alkaline, so that the effect of improving the leaching efficiency of thiosulfate is mainly achieved, the oxidation process is generally carried out under an acidic condition, the waste residue is in an acidic environment, and thiosulfate is unstable under the acidic condition and is easy to react with H+The reaction occurs to generate elemental sulfur and sulfur dioxide, thereby reducing the effective components of thiosulfate and reducing the leaching efficiency.
In the technical scheme of the invention, the thiosulfate solution mainly plays a role in dissolving Hg in waste residues after oxidation treatment2+And leaching of the compound, thiosulfate, to Hg2+Has strong leaching capacity.
In the technical scheme of the invention, the organic acid and the iodized salt mainly play a role in leaching mercury existing in the form of oxidized mercury in the waste residue. Organic acids adopted are mainlyTo perform three functions, on the one hand H+Reacts with oxidized mercury in the mercury-containing hazardous waste residue to form soluble Hg2+On the other hand, acid radical complex ions are provided, and on the third aspect, the acid environment of the mercury-containing hazardous waste residue is kept, so that the leaching of iodine salt is facilitated, and the mercury ion leaching efficiency is improved. The iodized salt mainly provides ligand iodide ions and has stronger coordination and complexation capacity on mercury ions, thereby improving the solubility of mercury compounds in the leaching solution.
The mixed solution of sodium sulfide and sodium hydroxide mainly plays a role in leaching mercury existing in the form of mercury sulfide in the mercury-containing dangerous waste residue. The mercury in the dangerous waste residue containing mercury is leached to the maximum extent by oxidizing and adopting a method of leaching different leaching solutions in multiple steps aiming at different forms of mercury, so that the aims of reducing the mercury content in the dangerous waste residue containing mercury, further reducing the leaching toxicity of the dangerous waste residue containing mercury and changing the dangerous waste residue containing mercury into common waste are fulfilled.
According to the technical scheme, firstly, proper oxidant solution is adopted to fully oxidize zero-valent mercury, organic mercury, monovalent mercury and the like in the mercury-containing hazardous waste residue into divalent mercury, so that subsequent leaching is facilitated. In the leaching process, the main active components of the adopted leaching solution are thiosulfate, organic acid, iodized salt, sodium sulfide and the like. Thiosulfate provides thiosulfate ions which can react with Hg in the waste residue2+Strong complexation occurs to form a stable water-soluble complex (stability constant 10)32.26) And (3) transferring a considerable part of mercury from the solid phase of the mercury-containing hazardous waste residue to the liquid phase, thereby leaching the mercury. Organic acid provides hydrogen ion and complex acid radical ion, and iodine salt provides I-The components play a remarkable synergistic effect on the leaching of mercury. The organic acid can react with HgO to release free mercury ions, and the organic carboxylate can play a role in coordination and complexation of the mercury ions. For example, the reaction formula is as follows: HgO +2H+→Hg2++H2And O. Meanwhile, the waste residue is in an acid environment due to the addition of the organic acid, so that the leaching of the iodized salt is facilitated, and the leaching efficiency of the iodized salt is higher under the condition of lower pH. I provided in iodonium salts-Can be mixed with Hg2+Form a very strong ligand when I-Excess of Hg2+Can form neutral HgI with it2 0Or negative HgI3 -，HgI4 2-. Where the tetraiodonium ligand is most stable, the presence of the ligand may increase the concentration of mercury in water; only mercury in the form of mercuric sulfide is basically left in the dangerous waste residue containing mercury after the leaching of thiosulfate, organic acid and iodized salt, and then the leaching is carried out by adopting a mixed solution of sodium sulfide and sodium hydroxide, wherein the sodium sulfide can react with the mercuric sulfide to generate a soluble mercuric sulfide compound Na2[HgS2]The main function of sodium hydroxide is to inhibit hydrolysis of sodium sulfide, and the addition of sodium hydroxide is not excessive, which would result in Na2[HgS2]The solubility decreases and the dissolution rate of HgS is slowed. In addition, the alkaline mixed solution can also play the following roles: (1) adjusting the pH value of the waste residue; (2) since the hydroxide form of mercury is more readily adsorbed than the Hg-Cl form, the OH continues to rise above pH 5-The concentration also increases, such that the activity of Hg (OH) Cl is greater than that of Hg (OH)2Higher activity and therefore, Hg in soil2+The amount of adsorption is reduced. So that the mixed solution of sodium sulfide and sodium hydroxide can further leach out residual adsorbed mercury by controlling the pH.
In the process of the method for reducing the content of mercury and the leaching toxicity in the mercury-containing hazardous waste residue through wet leaching, which is provided by the technical scheme of the invention, the synergistic relationship among chemical leaching agents can be embodied only by firstly adopting an oxidant solution for oxidation, then adopting thiosulfate for leaching, then adopting organic acid and iodized salt for leaching and finally adopting a mixed solution of sodium sulfide and sodium hydroxide for leaching, so that the optimal leaching effect is achieved.
The method for efficiently leaching the mercury-containing hazardous waste residue specifically comprises the following steps:
(1) crushing and grinding the dangerous waste residue containing mercury and sieving the dangerous waste residue with a 20-mesh sieve to remove larger impurities such as stones and the like;
(2) adding a proper amount of water into the screened dangerous waste residue fine particles containing mercury to keep the waste residue moist so as to facilitate various reactions, adding a prepared oxidant, uniformly stirring, heating to 50-100 ℃, and reacting for 20min to convert organic mercury and monovalent mercury in the dangerous waste residue containing mercury into divalent mercury;
(3) adding an alkaline material or an alkaline solution to adjust the pH of the waste residue to 7-8;
(4) adding thiosulfate solution, keeping the liquid-solid ratio at 5: 1-10: 1mL/g, and continuously leaching for 3-12 h;
(5) after solid-liquid separation, adding clear water into the dangerous waste residue containing mercury for cleaning, and treating and recycling the leached waste liquid and the cleaning wastewater;
(6) adding a mixed solution of organic acid and iodized salt into the cleaned dangerous waste residue containing mercury, keeping the liquid-solid ratio at 5: 1-10: 1mL/g, and continuously leaching for 3-12 h;
(7) after solid-liquid separation, adding clear water into the dangerous waste residue containing mercury for cleaning, and treating and recycling the leached waste liquid and the cleaning wastewater;
(8) adding a mixed solution of sodium sulfide and sodium hydroxide into the cleaned dangerous waste residue containing mercury, keeping the liquid-solid ratio at 2: 1-5: 1mL/g, and continuously leaching for 3-12 h;
(9) after solid-liquid separation, adding clear water into the dangerous waste residue containing mercury for cleaning, and treating and recycling the leached waste liquid and the cleaning wastewater.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) the leaching method can realize the high-efficiency leaching of various forms of mercury in the mercury-containing dangerous waste residue; such as zero-valent mercury, organic mercury, monovalent mercury, indissolvable mercury oxide, mercuric sulfide and the like can be effectively leached;
2) the synergistic effect among the leaching steps is strong, the mercury removing capability in the mercury-containing dangerous waste residue is strong, and the effect is good; the leaching effect of mercury is obviously improved under the synergistic action of oxidation, complexation and the like.
3) The leachate of the invention adopts organic acid, which has smaller requirements on leaching equipment compared with the existing inorganic acid, and the organic acid can be degraded by microorganisms in the waste residue, can not remain in the waste residue, can also provide hydrogen ions, can react with mercury in indissolvable forms such as HgO and the like to generate soluble mercury compounds, and simultaneously provides an acidic environment for leaching iodized salt;
4) according to the technical scheme, the mixed alkali liquor consisting of sodium sulfide and sodium hydroxide is used for leaching mercury sulfide which is extremely insoluble, so that the leaching efficiency is greatly improved;
5) according to the technical scheme, the oxidation and step-by-step leaching process is adopted aiming at the characteristic that the mercury-containing dangerous waste residue contains mercury in different forms, so that the leaching efficiency is greatly improved, the mercury content in the mercury-containing dangerous waste residue is reduced, the leaching toxicity of the mercury-containing dangerous waste residue is further reduced, the waste is changed into common waste, and the treatment cost of the mercury-containing waste is greatly reduced.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Taking waste residue left by smelting certain mercury ores in copper kernels in Guizhou, wherein the mercury content in the waste residue is up to 1150mg/kg, leaching the taken slag sample according to a sulfuric acid-nitric acid method (HJ/T299-2007) of solid waste leaching toxicity leaching method, wherein the mercury concentration in a leaching solution is 3.25mg/L and exceeds the mercury concentration limit value of 0.1mg/L in GB5085.3-2007 standard leaching toxicity identification of waste identification, and the mercury-containing dangerous waste residue is waste.
And naturally drying the waste residues, grinding and sieving by a 20-mesh sieve for later use. Respectively preparing an oxidant and each leaching solution, wherein the oxidant is prepared by adding 4% potassium persulfate solution into 5% HCl solution according to the volume ratio of 1:10, the concentration of thiosulfate solution is 0.1moL/L, the concentration of citric acid is 1moL/L, the concentration of potassium iodide is 0.1moL/L, the mass percent concentration of sodium sulfide is 5%, and the addition amount of sodium hydroxide is 1.5% of the dosage of sodium sulfide. Weighing 5g of pretreated waste residue into a 100mL centrifuge tube, adding deionized water to keep the waste residue wet, then adding a prepared potassium persulfate solution serving as an oxidant, controlling the molar ratio of potassium persulfate in the potassium persulfate solution to mercury in the waste residue to be not less than 2:1, uniformly stirring, and heating for 20min (the temperature is controlled at 80 ℃). Adding sodium hydroxide solution to adjust the pH of the waste residue to 7.5, adding 50mL of sodium thiosulfate solution, horizontally oscillating for 12h, centrifuging for 20min (rotating speed 3000r/min), discarding the supernatant, adding 10mL of water to the residual waste residue, oscillating for 30min, washing the leached waste residue, discarding the supernatant, adding 50mL of citric acid and potassium iodide mixed solution, continuously oscillating for 12h, centrifuging for 20min (rotating speed 3000r/min), discarding the supernatant, adding 10mL of water to the residual waste residue, oscillating for 30min, washing the leached waste residue, discarding the supernatant, adding 25mL of sodium sulfide and sodium hydroxide mixed solution, continuously oscillating for 12h, centrifuging for 20min (rotating speed 3000r/min), discarding the supernatant, adding 10mL of water to the residual waste residue, oscillating for 30min, washing the leached waste residue, discarding the supernatant, taking out the waste residue, air-drying, and determining the mercury content of the waste residue to be 67.68mg/kg, the content is greatly reduced, and the leaching rate reaches 94.11 percent. Leaching the solid waste according to a sulfuric acid-nitric acid method (HJ/T299-2007) of leaching toxicity leaching method of the solid waste, wherein the concentration of mercury in a leaching solution is 0.07mg/L and is lower than the limit value of the concentration of mercury in a waste identification standard leaching toxicity identification (GB5085.3-2007) by 0.1mg/L, and the mercury-containing dangerous waste residue is changed into general industrial solid waste after leaching treatment.
Comparative example 1
The same hazardous waste residue containing mercury as in example 1 was taken, air-dried, milled and sieved to prepare the same leaching solution as in example 1, respectively, and oxidation treatment was carried out without adding an oxidant, the following steps were the same as in example 1, and after air-dried treatment, the mercury content in the waste residue was determined to be 93.57mg/kg, which was greatly reduced, and the leaching rate reached 91.86%. Leaching the solid waste according to a sulfuric acid-nitric acid method (HJ/T299-2007) of leaching toxicity leaching method of the solid waste, wherein the concentration of mercury in a leaching solution is 0.11mg/L and is higher than the concentration limit value of mercury in a waste identification standard leaching toxicity identification (GB5085.3-2007) by 0.1mg/L, and the mercury-containing dangerous waste residue is still dangerous waste after leaching treatment.
Comparative example 2
The same hazardous waste residue containing mercury as in example 1 was taken, air-dried, milled and sieved, and the same oxidant and each leachate as in example 1 were prepared. Weighing 5g of the pretreated waste residue into a 100mL centrifuge tube, carrying out oxidation treatment in the same way as in example 1 without pH adjustment, carrying out the next leaching step in the same way as in example 1, and measuring the mercury content in the waste residue to be 95.21mg/kg after air drying treatment, wherein the mercury content is greatly reduced and the leaching rate reaches 91.72%. Leaching the solid waste according to a sulfuric acid-nitric acid method (HJ/T299-2007) of leaching toxicity leaching method of the solid waste, wherein the concentration of mercury in a leaching solution is 0.15mg/L and is higher than the concentration limit value of mercury in a waste identification standard leaching toxicity identification (GB5085.3-2007) by 0.1mg/L, and the mercury-containing dangerous waste residue is still dangerous waste after leaching treatment.
Comparative example 3
The same hazardous waste residue containing mercury as in example 1 was taken, and subjected to the same air drying, milling and screening treatments to prepare an oxidizing agent, a sodium thiosulfate solution, and a mixed solution of citric acid and potassium iodide, wherein the oxidizing agent was 4% potassium persulfate solution added to 5% HCl solution at a volume ratio of 1:10, the concentration of the sodium thiosulfate solution was 0.1moL/L, the concentration of citric acid was 1moL/L, and the concentration of potassium iodide was 0.1 moL/L. Weighing 5g of the pretreated waste residue into a 100mL centrifuge tube, and performing the following steps of oxidation, pH adjustment, sodium thiosulfate leaching, citric acid and potassium iodide leaching, water washing and the like in the process as same as the example 1, wherein the leaching is performed without using a mixed solution of sodium sulfide and sodium hydroxide, and the mercury content of the waste residue is determined to be 168.65mg/kg after air drying treatment, the mercury content is greatly reduced, and the leaching rate reaches 85.33%. Leaching the solid waste according to a sulfuric acid-nitric acid method (HJ/T299-2007) of leaching toxicity leaching method of the solid waste, wherein the concentration of mercury in a leaching solution is 0.35mg/L and is higher than the concentration limit value of mercury in a waste identification standard leaching toxicity identification (GB5085.3-2007) by 0.1mg/L, and the mercury-containing dangerous waste residue is still dangerous waste after leaching treatment.
Comparative example 4
The same hazardous waste residue containing mercury as in example 1 was taken, air-dried, milled and sieved to prepare an oxidant, a citric acid solution, a potassium iodide solution, and a mixed solution of sodium sulfide and sodium hydroxide, respectively, wherein the oxidant was 4% potassium persulfate solution added to 5% HCl solution in a volume ratio of 1:10, the citric acid concentration was 1moL/L, the potassium iodide concentration was 0.1moL/L, the sodium sulfide concentration was 5% by mass, and the sodium hydroxide addition was 1.5% of the sodium sulfide dosage. Weighing 5g of the pretreated waste residue into a 100mL centrifuge tube, wherein the following oxidation step is the same as that in the example 1, the pH regulation step and the sodium thiosulfate leaching step are not carried out, the rest leaching steps and the water washing step in the process are the same as those in the example 1, and the mercury content in the waste residue is determined to be 125.31mg/kg after air drying treatment, so that the mercury content is greatly reduced, and the leaching rate reaches 89.1%. Leaching the solid waste according to a sulfuric acid-nitric acid method (HJ/T299-2007) of leaching toxicity leaching method of the solid waste, wherein the concentration of mercury in a leaching solution is 0.25mg/L and is higher than the concentration limit value of mercury in a waste identification standard leaching toxicity identification (GB5085.3-2007) by 0.1mg/L, and the mercury-containing dangerous waste residue is still dangerous waste after leaching treatment.
Example 2
The same hazardous waste residue containing mercury as in example 1 was taken, air-dried, milled and sieved, and an oxidant and each leachate were prepared, wherein the oxidant was 4% sodium persulfate solution added to 5% HCl solution at a volume ratio of 1:10, the leachate had a concentration of 0.1moL/L ammonium thiosulfate, a concentration of 1moL/L citric acid, a concentration of 0.1moL/L sodium iodide, a concentration of 5% sodium sulfide by mass, and an amount of sodium hydroxide added was 1.5% of the amount of sodium sulfide. Weighing 5g of the pretreated waste residue into a 100mL centrifuge tube, wherein the following steps are the same as those in example 1, and the mercury content of the waste residue is determined to be 79.56mg/kg after air drying treatment, so that the mercury content is greatly reduced, and the leaching rate reaches 93.08%. Leaching the solid waste according to a sulfuric acid-nitric acid method (HJ/T299-2007) of leaching toxicity leaching method of the solid waste, wherein the concentration of mercury in a leaching solution is 0.081mg/L which is lower than the concentration limit value of mercury in a waste identification standard leaching toxicity identification (GB5085.3-2007), and the mercury-containing dangerous waste residue is changed into general industrial solid waste after leaching treatment.
Example 3
The same mercury as in example 1 was taken, and subjected to the same air drying, milling and screening treatments, and an oxidizing agent and each leachate were respectively prepared, wherein the oxidizing agent was 4% potassium persulfate solution added to 5% HCl solution at a volume ratio of 1:10, the leachate had a potassium thiosulfate concentration of 0.1moL/L, a tartaric acid concentration of 1moL/L, a potassium iodide concentration of 0.1moL/L, a sodium sulfide concentration of 5% by mass, and a sodium hydroxide addition amount of 1.5% of the sodium sulfide amount. Weighing 5g of the pretreated waste residue into a 100mL centrifuge tube, wherein the following steps are the same as those in example 1, and the mercury content in the waste residue is 83.39mg/kg after air drying treatment, so that the mercury content is greatly reduced, and the leaching rate reaches 92.75%. Leaching the solid waste according to a sulfuric acid-nitric acid method (HJ/T299-2007) of leaching toxicity leaching method of the solid waste, wherein the concentration of mercury in a leaching solution is 0.075mg/L and is lower than the limit value of the concentration of mercury in a waste identification standard leaching toxicity identification (GB5085.3-2007) by 0.1mg/L, and the mercury-containing dangerous waste residue is changed into general industrial solid waste after leaching treatment.
Claims (9)
1. A method for efficiently removing mercury from dangerous waste residue containing mercury by a full-wet method is characterized by comprising the following steps: the method comprises the following steps:
1) crushing, grinding and sieving the mercury-containing hazardous waste residue, and taking fine mercury-containing hazardous waste residue particles under the sieve;
2) adding water into the mercury-containing hazardous waste residue fine particles for moisture preservation, adding an oxidant solution, stirring and heating for oxidation treatment;
3) adjusting the pH value of the mercury-containing hazardous waste residue fine particles after oxidation treatment to be more than 7;
4) adding thiosulfate solution for leaching, and then adding water for cleaning;
5) adding a mixed solution of organic acid and iodized salt for leaching, and then adding water for cleaning;
6) adding a mixed solution of sodium sulfide and sodium hydroxide for leaching, and then adding water for cleaning; the mass percentage concentration of sodium sulfide in the mixed solution of sodium sulfide and sodium hydroxide is 5-10%, and the mass of sodium hydroxide is 1-2% of the mass of sodium sulfide.
2. The method for efficiently removing mercury from dangerous mercury-containing waste residues by the full-wet method according to claim 1, wherein the method comprises the following steps: the oxidant solution is persulfate solution, and the mass percentage concentration of the persulfate solution is 0.1-1%.
3. The method for efficiently removing mercury from dangerous mercury-containing waste residues by the full-wet method according to claim 2, wherein the method comprises the following steps: the molar ratio of the persulfate to the mercury element in the mercury-containing hazardous waste residue is not less than 2: 1;
the persulfate includes potassium persulfate and/or sodium persulfate.
4. The method for efficiently removing mercury from dangerous mercury-containing waste residues by the full-wet method according to any one of claims 1 to 3, wherein the method comprises the following steps:
the concentration of the thiosulfate solution is 0.01-0.3 mol/L.
5. The method for efficiently removing mercury from dangerous mercury-containing waste residues by the full-wet method according to claim 4, wherein the method comprises the following steps: the thiosulfate comprises at least one of sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, calcium thiosulfate and magnesium thiosulfate.
6. The method for efficiently removing mercury from dangerous mercury-containing waste residues by the full-wet method according to any one of claims 1 to 3, wherein the method comprises the following steps:
the concentration of the organic acid in the mixed solution of the organic acid and the iodized salt is 0.5-1 mol/L, and the concentration of the iodized salt is 0.01-0.3 mol/L;
the organic acid comprises at least one of citric acid, tartaric acid and oxalic acid;
the iodine salt comprises at least one of potassium iodide, sodium iodide, magnesium iodide and ammonium iodide.
7. The method for efficiently removing mercury from dangerous mercury-containing waste residues by the full-wet method according to any one of claims 1 to 3 and 5, wherein the method comprises the following steps:
and 4) in the process of leaching the thiosulfate solution, the liquid-solid ratio is 5: 1-10: 1mL/g, and the leaching time is 3-12 h.
8. The method for efficiently removing mercury from dangerous mercury-containing waste residues by the full-wet method according to any one of claims 1 to 3 and 5, wherein the method comprises the following steps:
and step 5), in the leaching process of the mixed solution of the organic acid and the iodized salt, the liquid-solid ratio is 5: 1-10: 1mL/g, and the leaching time is 3-12 h.
9. The method for efficiently removing mercury from dangerous mercury-containing waste residues by the full-wet method according to any one of claims 1 to 3 and 5, wherein the method comprises the following steps: and 6) in the leaching process of the mixed solution of sodium sulfide and sodium hydroxide, the liquid-solid ratio is 2: 1-5: 1mL/g, and the leaching time is 3-12 h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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