CN107597787B - Method for efficiently stabilizing mercury-containing waste residues - Google Patents
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Abstract
The invention discloses a method for efficiently stabilizing mercury-containing waste residues, which comprises the following steps: 1) breaking the waste residue containing mercuryCrushing and sieving, and taking mercury residue fine particles under the sieve; 2) adding water into the mercury slag fine particles for moisturizing, adding an oxidant solution, stirring and heating for oxidation reaction; 3) adding a sulfide solution into the mercury slag fine particles to carry out a vulcanization reaction; 4) adding ferrous salt into mercury slag fine grains to precipitate excessive S2‑Adding clay minerals and humus into the mercury slag fine particles for adsorption, 6) adding a pH regulator into the mercury slag fine particles to regulate the pH value of mercury-polluted soil to 6-7, and maintaining for more than 3 days; the method can simultaneously stabilize and solidify various forms of mercury in the mercury-containing waste residue, has good stabilizing effect and short period, adopts wide sources of raw materials of the medicament, has low cost and is beneficial to wide application.
Description
Technical Field
The invention relates to a heavy metal waste residue treatment method, in particular to a method for stabilizing mercury-containing waste residue, and belongs to the technical field of heavy metal waste residue treatment.
Background
In recent years, with the rapid development of industry and agriculture, mercury is discharged in large quantity in the production and use processes, and the national records of dangerous waste list classifies mercury-containing waste as HW29 dangerous waste. The mercury-containing waste residue mainly refers to mercury-containing solid waste produced 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 waste residue, and has important significance for environmental management and human health protection in China.
The existing treatment technology of the mercury-containing waste residue mainly comprises resource recovery and safe landfill, wherein one method of the resource recovery is to transfer mercury into a gas phase through heat treatment and then recover the mercury through cooling, and the other method is to transfer the mercury into a liquid phase through chemical leaching and then recover the mercury through ion exchange and other methods. The resource recovery method is rarely applied to large-scale mercury-containing waste residue treatment due to low value and high treatment cost of the recovered mercury, the most mature and reliable mercury-containing waste residue treatment technology is safe landfill, and most mercury-containing waste residues are safe landfill after being treated by a solidification/stabilization method due to high mercury content. The solidification/stabilization process is a combination of techniques that immobilize contaminants in waste by physical and chemical action. The stabilizing and solidifying agent can react with heavy metal pollutants in the waste residue chemically or physically, so that the heavy metal pollutants are converted into a form which is not easy to dissolve, has weak migration capacity and is less toxic. In the prior art, researches on stabilizing agents and repairing methods of mercury-contaminated soil are more, for example, chinese patent (CN105414166A) discloses a repairing method of mercury-contaminated soil, specifically, soil on the surface of mercury-contaminated soil above the ground is ploughed, air-dried, ground and sieved to obtain pretreated surface soil; fully and uniformly mixing a passivating agent consisting of bentonite, hydroxyapatite, ammonium thiosulfate and calcium hydroxide with the treated surface soil, standing for 10-20 days until 70% of mercury content in the surface soil is fixed, and completing the repairing of the passivating agent; leveling surface soil, planting Indian kale, dissolving calcium thiosulfate in water in the vigorous growth period of the Indian kale, uniformly spraying the solution into soil around the root system of the Indian kale, and finally harvesting the Indian kale. Chinese patent (CN 105598145A) discloses an in-situ remediation method for mercury-contaminated soil, which selects three passivators of biochar, calcium polysulfide and sodium selenite, can effectively improve the soil microenvironment after the biochar is mixed and applied to the soil, greatly reduces the migration of mercury in the alkaline-biased and strong-reducibility soil, and can absorb a large amount of mercury in the soil by the biochar with strong specific surface and porous structure and complex organic functional groups; pouring calcium polysulfide solution into the soil can further promote the mineralization of mercury, enhance the biological activity of the microenvironment of the soil at the roots of the crops after the crops are planted, selectively apply sodium selenite solution, and weaken the biological effectiveness of the crops by utilizing the antagonistic effect of selenium and mercury. After three passivation substances are added for treatment, the mercury content in crops is obviously reduced. Chinese patent (CN 104998894A) discloses a mercury-contaminated soil solidification and stabilization method, which comprises a chlorine salt adding process, a pH adjusting process, a mixing process, an activator adding process, a digestion forming process and a crushing treatment process. The method can be used for solidifying and stabilizing the mercury-polluted soil with different pollution degrees, and can also be used for synergistically solidifying and stabilizing other heavy metals in the polluted soil. The cured stabilized product may be backfilled or used for other purposes. However, the mercury-containing waste residue belongs to mercury-enriched residue, the mercury content is complex, the content is high, and the agent and the method which are generally suitable for repairing mercury-polluted soil are not necessarily suitable for stabilizing the mercury-containing waste residue.
Disclosure of Invention
Aiming at the defects of the treatment method of the mercury-containing waste residue in the prior art, the invention aims to provide the method which can simultaneously stabilize and solidify various forms of mercury in the mercury-containing waste residue, has good stabilization effect and short period, adopts wide sources of medicament raw materials, has low cost and is beneficial to wide application.
In order to achieve the technical purpose, the invention provides a method for efficiently stabilizing mercury-containing waste residue, which comprises the following steps:
1) crushing and sieving the mercury-containing waste residues, and taking mercury residue fine particles under the sieve;
2) adding water into the mercury slag fine particles for moisturizing, adding an oxidant solution, stirring and heating for oxidation reaction;
3) adding a sodium sulfide solution into the mercury slag fine particles to carry out a vulcanization reaction;
4) adding ferrous salt into mercury slag fine grains to precipitate excessive S2-；
5) Adding clay minerals and humus into the mercury slag fine particles for adsorption;
6) adding a pH regulator into the mercury slag fine particles to regulate the pH value of the mercury-polluted soil to 6-7, and maintaining for more than 3 days;
wherein,
the oxidant is measured by more than 2 times of the molar weight of mercury in the mercury-containing waste residue;
the sulfide salt is measured by more than 2 times of the molar weight of mercury in the mercury-containing waste residue;
the ferrous salt is measured by 0.5 to 3 percent of the mass of the waste residue containing mercury;
the clay mineral and the humus are measured by 2 to 15 percent of the mass of the mercury-containing waste residue;
and the pH regulator is used for regulating the pH value of the mercury-containing waste residue to be 6-7.
In a preferred embodiment, the oxidizing agent is a persulfate; more preferably potassium persulfate and/or sodium persulfate; further preferred is potassium persulfate.
In a preferred scheme, the sulfide salt comprises at least one of sodium sulfide, ammonium sulfide and potassium sulfide; sodium sulfide is more preferred.
In a preferred scheme, the ferrous salt comprises at least one of ferrous sulfate, ferrous chloride and ferrous nitrate; ferrous nitrate is more preferred.
In a preferred embodiment, the clay mineral includes at least one of bentonite, zeolite, sepiolite, illite, montmorillonite, and attapulgite. More preferably illite and/or montmorillonite.
In a preferred embodiment, the pH adjuster includes at least one of calcium oxide, calcium hydroxide, and calcium carbonate.
In the preferable scheme, the grain size of the mercury polluted soil under the sieve is less than or equal to 2 cm.
In the preferable scheme, the curing time is 3-7 days.
In the preferable scheme, the temperature of the oxidation reaction is 50-100 ℃.
It is within the understanding of one skilled in the art that the oxidizing agent solution of the present invention will generally be added with an appropriate amount of acid as a catalyst to increase the efficiency of the oxidation. For example, a potassium persulfate solution of about 4% is added to a 5% HCl solution in a volume ratio of 1: 10. In order to ensure that the organic mercury, the univalent mercury and other low-valent mercury in the mercury-containing waste residue can be completely converted into Hg2+The effective components in the persulfate are excessive relative to the mercury element in the waste residue.
The sulfide salt of the invention is used as a reagent for stabilizing mercury, and is used for ensuring Hg in a reaction system2+Can completely generate precipitate, and the adding amount of the sulfide salt is at least 2:1 relative to the molar weight ratio of mercury element in the waste residue.
The inventionThe ferrous salt has three main functions, firstly, the excessive S existing in the reaction system can be removed2-Precipitate is formed to prevent re-dissolution of mercury sulfide, and second, excess oxidant is consumed to remove excess Fe2+Oxidizing to obtain hydrated iron oxide colloid, adsorbing and coprecipitating to further remove mercury and excessive Fe2+The existence of the catalyst enables the waste residue environment to be under a reducing condition, so that the generation of mercury sulfide is more facilitated.
The clay mineral and the humus have the effect of synergistically adsorbing trace mercury.
The pH regulator can control the pH of the waste residue to be 6-7, and is beneficial to the stable existence of the whole system and the mercuric sulfide under the condition that the pH is 6-7.
The method for stabilizing the mercury-containing waste residue provided by the technical scheme of the invention is mainly provided aiming at the safe disposal of the mercury-containing waste residue, the mercury-containing 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 higher toxicity. The method adopts the oxidant, the composite stabilizer and the pH regulator to jointly treat the mercury-containing waste residue, and mainly realizes the stabilization of the mercury in the waste residue by the synergistic effect of chemical oxidation, precipitation, adsorption and the like, so that the mercury is stabilized in the stable form of mercury sulfide, the mobility and the bioavailability of the mercury in the waste residue are greatly reduced, the stabilization of the mercury is a chemical curing process and does not depend on the activity of microorganisms, and therefore, the method is not sensitive to heavy metal toxicity, waste residue property and wide in applicability.
In the method, the synergistic interaction among the components in the oxidant, the composite stabilizer and the pH regulator is obvious, and the stabilization effect of mercury is greatly improved. Based on consideration of Hg2+Is easier to react with S2-Forming stable HgS, firstly oxidizing low-valent mercury such as organic mercury and monovalent mercury in soil into divalent mercury by adopting oxidants such as persulfate, and then utilizing sulfide and Hg2+Reacting to form stable mercuric sulfide precipitate, but adding excessive S during actual treatment2-To ensure that mercury is fully immobilized, but excess sulfur will cause the HgS to further form a soluble HgS2-And then dissolved again. And the addition of ferrous salt can make the S excessive2-To form a FeS precipitate, with Fe2+The excessive oxidant can be consumed and oxidized to generate hydrated iron oxide, and the hydrated iron oxide can remove mercury through surface adsorption and coprecipitation; further, Fe2+The existence of the mercury sulfide in the waste residue enables the waste residue environment to be under a reducing condition, so that the mercury sulfide is more favorable for generating mercury sulfide, and the mercury sulfide is very stable and exists in the waste residue for a long time. But excessive Fe2+Can cause new problems, and is easy to hydrolyze to release H+Ions, changing the waste residue into acid: 4Fe2++O2+6H2O→4FeOOH+8H+And adjusting the pH value of the waste residue by adding an alkaline substance to finally stabilize the pH value of the waste residue to be 6-7, wherein the pH value is the best pH value for stabilizing mercury in the waste residue. In addition, the addition of clay minerals and humus can synergistically adsorb residual mercury, thereby further strengthening the stabilization effect.
The agents adopted in the high-efficiency stabilization process of the mercury-containing waste residue are added according to a proper proportion and sequence according to the mercury content in the waste residue.
The medicament adopted by the method of the invention, such as sulfide salt, ferrous salt, clay minerals, humus and other materials, are all solid particles or powder, when in use, the sulfide salt is added firstly, the mixture is stirred uniformly and reacts for a period of time, then the ferrous salt is added, finally the clay minerals, humus and other adsorbing materials are added, the materials are added after being mixed, otherwise, the sulfide salt reacts with the ferrous salt to reduce effective components, thereby reducing the stable effect.
The pH regulator of the invention is alkaline substances such as calcium oxide, calcium hydroxide, calcium carbonate and the like, and is solid powder.
The method for stabilizing the mercury-containing waste residue comprises the following specific steps:
(1) crushing and screening the mercury-containing waste residues until the particle size is less than or equal to 2cm, and removing larger impurities such as stones;
(2) adding a proper amount of water into the mercury-containing waste residues to keep the waste residues moist so as to facilitate various reactions, adding a prepared oxidant solution (added in a solution form and added with a proper amount of acid as a catalyst), uniformly stirring, and heating for 20min (the temperature is controlled between 50 and 100 ℃) to convert organic mercury and monovalent mercury in the waste residues into divalent mercury;
(3) adding sulfide salt which can be added in a solid form or prepared into solution, and uniformly stirring to ensure that Hg in the waste residue is added2+Completely converted into HgS precipitate;
(4) ferrous salt (solid) is added and stirred evenly to lead the excessive S2-FeS precipitate formed with excess Fe2+Oxidizing to generate hydrated iron oxide, and further removing mercury and Fe by surface adsorption and coprecipitation of iron oxide2+The existence of the mercury sulfide leads the whole environment to be under the reducing condition, thus being more beneficial to the generation of the mercury sulfide and being very stable and existing in the waste residue for a long time;
(5) adding clay minerals and humus, stirring uniformly, and further strengthening the stabilization effect;
(6) adding alkaline substances, uniformly stirring, adjusting the pH value of the waste residue to 6-7, and if the pH value of the waste residue is within the range of 6-7 after the steps, avoiding the step, and finally curing for 3-7 days.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) the method can realize the high-efficiency stabilization treatment of various forms of mercury in the mercury-containing waste residue; such as elementary mercury, organic mercury, monovalent mercury and the like can be effectively fixed.
2) The method of the invention adopts various medicaments which have strong capability of synergy among the components in the using process and have good effect of stabilizing mercury in the mercury-containing waste residue. The stabilizing and fixing effect on mercury is obviously improved under the synergistic action of oxidation, precipitation, adsorption and the like, and the efficient stabilizing and curing of mercury can be realized.
3) The method of the invention has the advantages of wide source of the adopted medicament raw materials, low cost and contribution to popularization and use.
4) The method can realize the rapid and efficient fixation of various forms of mercury in the mercury-containing waste residues through simple operation steps, can achieve a good stable effect after being generally maintained for 3 days, and leaches according to the horizontal oscillation method of the solid waste leaching toxicity leaching method (HJ557-2009), wherein the leaching concentration is lower than 0.25mg/L, thereby meeting the concentration limit of the hazardous waste landfill pollution control standard (GB18598-2001) which allows the mercury to enter a landfill site.
5) The method of the invention fixes the mercury in the mercury-containing waste residue through chemical stabilization, and does not depend on the activity of microorganisms, thereby being insensitive to heavy metal toxicity, waste residue property and wide applicability.
Detailed Description
The following specific 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 hazardous waste, and the mercury-containing waste residue is hazardous waste. Leaching the slag sample according to a solid waste leaching toxicity leaching method horizontal oscillation method (HJ557-2009), wherein the concentration of mercury in the leaching solution is 1.68mg/L and exceeds the concentration limit value of 0.25mg/L allowed to enter a landfill site in a hazardous waste landfill pollution control standard (GB18598-2001), and stabilizing and solidifying treatment is carried out to ensure that the mercury concentration reaches the site entry standard.
(1) Crushing and screening the mercury-containing waste residue until the particle size is less than or equal to 2cm, and removing larger impurities such as stones;
(2) adding a proper amount of water into the mercury-containing waste residue to keep the mercury-containing waste residue moist so as to facilitate various reactions, adding a prepared oxidant (4% of potassium persulfate solution is added into 5% of HCl solution, the volume ratio is 1:10), controlling the molar ratio of effective components in the potassium persulfate to mercury elements in the waste residue to be not less than 2:1, uniformly stirring, and heating for 20min (the temperature is controlled at 80 ℃) so as to convert organic mercury and monovalent mercury in the waste residue into divalent mercury;
(3) adding 5% sodium sulfide solution, wherein the adding amount of sodium sulfide is that the molar weight ratio of sulfur element to mercury element in waste residue is 2:1,stirring evenly, reacting for 30min to ensure Hg in the waste residue2+Completely converted into HgS precipitate;
(4) adding ferrous nitrate, wherein the adding amount is 2% of the mass of the waste residue, uniformly stirring, and reacting for 15 min;
(5) adding illite, montmorillonite and humus in a mass ratio of 1:1:1, wherein the total addition amount is 10% of the mass of the soil, and uniformly stirring;
(6) adding calcium hydroxide, stirring uniformly, adjusting the pH value of the waste residue to 6-7, and if the pH value of the soil after the steps is within the range of 6-7, the step can be avoided;
(7) and (3) after curing for 3 days, leaching according to a solid waste leaching toxicity leaching method horizontal oscillation method (HJ557-2009), wherein the concentration of mercury in the leachate is 0.09mg/L, and the concentration limit of the mercury allowed to enter a landfill site in hazardous waste landfill pollution control standard (GB18598-2001) is 0.25 mg/L.
Example 2
Taking the same waste residue as in example 1, crushing and screening the same waste residue, adding a proper amount of water into the waste residue to keep the waste residue wet, adding a prepared oxidant (4% sodium persulfate solution is added into 5% HCl solution, the volume ratio is 1:10), controlling the molar ratio of the effective components in the sodium persulfate to the mercury elements in the waste residue to be not less than 2:1, stirring the mixture uniformly, heating the mixture for 20min (the temperature is controlled to be 80 ℃), performing the rest steps of the method for maintaining the waste residue for 3 days, leaching the waste residue according to a solid waste leaching toxicity leaching method horizontal oscillation method (HJ557-2009), wherein the concentration of mercury in a leachate is 0.13mg/L, which is higher than that in example 1, but can meet the limit of 0.25mg/L of concentration allowed to enter a landfill site in a hazardous waste landfill pollution control standard (GB 18598-2001).
Example 3
Taking the same waste residue as in example 1, carrying out the same crushing and screening treatment, adding the same oxidant as in example 1 to carry out the same oxidation reaction, adding a 5% potassium sulfide solution, wherein the adding amount of potassium sulfide is that the molar weight ratio of sulfur elements to mercury elements in the waste residue is 2:1, uniformly stirring, reacting for 30min, adding ferrous chloride, the adding amount is 2% of the mass of the waste residue, uniformly stirring, and reacting for 15 min; adding bentonite, zeolite and humus in a mass ratio of 1:1:1, wherein the total addition amount is 10% of the mass of the waste residue, and uniformly stirring; the subsequent pH adjustment was carried out in the same manner as in example 1, and after 3 days of curing, leaching was carried out according to the "method of toxic leaching by solid waste leaching" horizontal shaking (HJ557-2009) method, whereby the concentration of mercury in the leachate was 0.15mg/L, which was higher than that in example 1, but the limit of 0.25mg/L on the concentration allowed to enter the landfill in the "pollution control Standard for hazardous waste landfill" (GB18598-2001) was satisfied.
Comparative example 1
Taking the same waste residue as in the embodiment 1, carrying out the same crushing and screening treatment, adding the same oxidant as in the embodiment 1 to carry out the same oxidation reaction, then adding a 5% sodium sulfide solution, wherein the adding amount of the sodium sulfide is that the molar weight ratio of sulfur elements to mercury elements in the waste residue is 1:1, uniformly stirring, reacting for 30min, carrying out the next steps as in the embodiment 1, carrying out leaching according to a solid waste leaching toxicity leaching method horizontal oscillation method (HJ557-2009) after curing for 3 days, wherein the concentration of mercury in a leaching solution is 0.38mg/L which is higher than the value in the embodiment 1, and the concentration limit allowed to enter a landfill site in a hazardous waste landfill pollution control standard (GB18598-2001) cannot be met.
Comparative example 2
Taking the same waste residue as the embodiment 1, crushing and screening the waste residue, carrying out oxidation treatment without adding an oxidant, carrying out the rest steps in the same manner as the embodiment 1, maintaining the waste residue for 3 days, and then leaching the waste residue according to a solid waste leaching toxicity leaching method horizontal oscillation method (HJ557-2009), wherein the concentration of mercury in the leachate is 0.45mg/L, which is higher than the value in the embodiment 1, and the concentration limit of the mercury allowed to enter a landfill site in a hazardous waste landfill pollution control standard (GB18598-2001) cannot be met.
Comparative example 3
Taking the same waste residue as the embodiment 1, crushing and screening the waste residue, adding the same oxidant as the embodiment 1 to perform the same oxidation reaction, simultaneously adding a sodium sulfide solution, ferrous nitrate, illite, montmorillonite and humus, stirring the mixture uniformly, adding calcium hydroxide to adjust the pH value to 6-7, curing the mixture for 3 days, and leaching the mixture according to a horizontal oscillation method of a solid waste leaching toxicity leaching method (HJ557-2009), wherein the concentration of mercury in a leaching solution is 0.82mg/L which is far higher than that in the embodiment 1 and can not meet the concentration limit of hazardous waste landfill pollution control standard (GB18598-2001) which allows the mercury to enter a landfill.
Claims (8)
1. A method for efficiently stabilizing mercury-containing waste residues is characterized by comprising the following steps: the method comprises the following steps:
1) crushing and sieving the mercury-containing waste residues, and taking mercury residue fine particles under the sieve;
2) adding water into the mercury slag fine particles for moisturizing, adding an oxidant solution, stirring and heating for oxidation reaction;
3) adding a sulfide solution into the mercury slag fine particles to carry out a vulcanization reaction;
4) adding ferrous salt into mercury slag fine grains to precipitate excessive S2-；
5) Adding clay minerals and humus into the mercury slag fine particles for adsorption;
6) adding a pH regulator into the mercury slag fine particles to regulate the pH of the mercury slag fine particles to 6-7, and maintaining for more than 3 days; wherein,
the oxidant is measured by more than 2 times of the molar weight of mercury in the mercury-containing waste residue; the oxidant comprises potassium persulfate and/or sodium persulfate;
the sulfide salt is measured by more than 2 times of the molar weight of mercury in the mercury-containing waste residue;
the ferrous salt is measured by 0.5 to 3 percent of the mass of the waste residue containing mercury;
the clay mineral and the humus are measured by 2 to 15 percent of the mass of the mercury-containing waste residue;
and the pH regulator is used for regulating the pH value of the mercury-containing waste residue to be 6-7.
2. The method for efficiently stabilizing mercury-containing waste residue according to claim 1, wherein the method comprises the following steps: the sulfide salt comprises at least one of sodium sulfide, ammonium sulfide and potassium sulfide.
3. The method for efficiently stabilizing mercury-containing waste residue according to claim 1, wherein the method comprises the following steps: the ferrous salt comprises at least one of ferrous sulfate, ferrous chloride and ferrous nitrate.
4. The method for efficiently stabilizing mercury-containing waste residue according to claim 1, wherein the method comprises the following steps: the clay mineral includes at least one of bentonite, zeolite, sepiolite, illite, montmorillonite, and attapulgite.
5. The method for efficiently stabilizing mercury-containing waste residue according to claim 1, wherein the method comprises the following steps: the pH regulator comprises at least one of calcium oxide, calcium hydroxide and calcium carbonate.
6. The method for efficiently stabilizing the mercury-containing waste residue according to any one of claims 1 to 5, characterized by comprising the following steps: the grain size of the mercury residue under the sieve is less than or equal to 2 cm.
7. The method for efficiently stabilizing the mercury-containing waste residue according to any one of claims 1 to 5, characterized by comprising the following steps: the curing time is 3-7 days.
8. The method for efficiently stabilizing the mercury-containing waste residue according to any one of claims 1 to 5, characterized by comprising the following steps:
the temperature of the oxidation reaction is 50-100 ℃.
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| CN111570469A (en) * | 2020-05-13 | 2020-08-25 | 中信环境技术（广州）有限公司 | Treatment method of mercury-containing waste |
| CN112961679A (en) * | 2021-02-01 | 2021-06-15 | 博天环境集团股份有限公司 | Repairing agent and method for stably repairing mercury-polluted soil by adopting same |
| CN114713594B (en) * | 2022-04-07 | 2023-05-23 | 生态环境部南京环境科学研究所 | Molten slag utilization device for dangerous waste incineration and use method thereof |
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| CN102580979A (en) * | 2012-02-09 | 2012-07-18 | 中国科学院东北地理与农业生态研究所 | Solidification/stabilization method for mercury-containing hazardous waste |
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