CN111330427A - Application of metal sulfide mercury removal agent in washing and removing mercury in flue gas - Google Patents
Application of metal sulfide mercury removal agent in washing and removing mercury in flue gas Download PDFInfo
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- CN111330427A CN111330427A CN202010205930.6A CN202010205930A CN111330427A CN 111330427 A CN111330427 A CN 111330427A CN 202010205930 A CN202010205930 A CN 202010205930A CN 111330427 A CN111330427 A CN 111330427A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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Abstract
The invention discloses an application of a metal sulfide mercury removal agent in washing and removing mercury in flue gas. The invention uses metal sulfide mercury removing agent as mercury removing medium, and adds the mercury removing agent into flue gas washing device or wet dust removing device to form suspension liquid, which is mixed with elementary mercury (Hg) in flue gas0) The mercury is fully contacted with the mercury to be converted into stable mercury sulfide, and the elemental mercury (Hg) in the flue gas is realized0) The removal is efficient. The mercury removing agent adopted by the invention has high mercury removing efficiency, simple synthesis method, easily obtained raw materials, lower cost, mechanical property, acid resistance, water resistance and SO resistance2Good performance, simple technical operation, and no change of production process and existing pollutant control system. The components of the mercury removing agent are similar to those of the smelting raw materials, and the mercury removing agent after mercury recovery can be used as a metallurgical raw material, so that the mercury removing agent has no secondary pollution and has wide market application prospect.
Description
Technical Field
The invention belongs to the technical field of environmental pollution prevention and purification, and particularly relates to an application of a metal sulfide mercury removal agent in washing and removing mercury in flue gas.
Background
Mercury is an environmental pollutant with high toxicity, high corrosivity, high volatility, biological enrichment and easy migration and diffusivity. According to the 2018 global mercury pollution report newly issued by the United nations environmental planning agency (UNEP), the mercury emitted by human activities in the atmosphere exceeds 2500 tons/year and accounts for more than 80 percent of the total mercury emission in the nature, wherein the mercury emission mainly comprises the mercury emission in the industries of metallurgy industry, combustion of fossil fuels, cement production, petrochemical industry, garbage treatment and the like. The Water guarantee convention of 8 months in 2017 formally takes effect in 128 countries all over the world, and the restriction and reduction of artificial mercury pollutant emission become a wide consensus of the international society.
There are three main forms of mercury, including gaseous elemental mercury (Hg)0) Mercury (Hg) in its oxidized state2+) And particulate mercury (Hg)P) In which granular mercury (Hg) is presentp) Can be removed by particle impurity removing equipment in the process of flue gas purification, and oxidized mercury (Hg)2+) Can be removed by a flue gas washing device or a wet dust removal device, and gaseous elementary mercury (Hg)0) Low melting point, high volatility, and almost no water (solubility about 50 mug/L), and Hg is difficult to be washed or dedusted by the existing washing or dedusting equipment0Capture, so that the gaseous elementary mercury (Hg)0) The direct discharge of (A) causes great harm to the environment. Therefore, how to effectively control Hg0Has become an important issue to be solved at present.
The demercuration method used at home and abroad mainly comprises an activated carbon adsorption method, a solution absorption method, a low-temperature separation method and the like. The activated carbon adsorbent is a mature commercial demercuration medium, is widely used in the field of coal smoke demercuration, but has high cost, large consumption and expensive operation cost; the mercury adsorption capacity and the adsorption rate of the commercial activated carbon are small, so that the mercury emission standard which is stricter day by day is difficult to meet; the mercury is mainly physically adsorbed on the surface of the activated carbon, so that the activated carbon is easy to release mercury again when exposed to the environment, and secondary pollution to the environment is easy to generate; the mercury removal efficiency of commercial activated carbon is severely limited by the smoke conditions, acid resistance, water resistance and SO resistance2The performance is poor, the method is not suitable for being used in washing equipment or wet dust removal equipment, and the defects also limit the method in high SO2The use of a flue gas purification process. The solution absorption demercuration method mainly comprises the Boleton chlorination method, the potassium iodide method, the mercury sulfate method and the like. Although the solution absorption demercuration method has good demercuration effect, the demercuration solution is generally corrosive and easy to saturate, and has serious pollution to the environment, higher operation cost and higher requirement on equipment; oxidized mercury (Hg) in demercuration solution2+) Is susceptible to being influenced by smoke components and is reduced into gaseous elemental mercury (Hg)0) Resulting in the reduction of demercuration efficiency and secondary pollution to the environment.
Disclosure of Invention
In order to overcome the defects and shortcomings of mercury removal by commercial activated carbon adsorption and mercury removal by solution absorption, the invention provides an application of a metal sulfide mercury removal agent in the aspect of washing and removing mercury in flue gas. The metal sulfide mercury removing agent is used for washing and removing mercury in flue gas, and is efficient, economical and environment-friendly.
The invention utilizes the metal sulfide as the mercury removal medium, in the flue gas washing process, the metal sulfide mercury removal agent is added into the flue gas washing device or the wet dust removal device to form suspension, the metal sulfide mercury removal agent can be efficiently combined with mercury in gas and liquid phases to convert the mercury into stable mercury sulfide, thereby realizing Hg in the flue gas0High-efficiency removal.
The technical scheme of the invention is specifically introduced as follows:
the invention provides an application of a metal sulfide mercury removal agent in washing and removing mercury in flue gas.
Preferably, the application method is as follows: forming metal sulfide mercury removing agent into suspension in a washing device or a wet dust removal device, and removing Hg in flue gas0Conversion to stabilized mercury sulfide to realize Hg0And (4) washing and removing.
Preferably, the metal sulfide mercury removing agent is selected from metal sulfides or a combination of the metal sulfides, the metal sulfides are monobasic metal sulfides such as copper sulfide, molybdenum sulfide, zinc sulfide, lead sulfide, manganese sulfide and the like, and binary or multi-element metal sulfides such as iron sulfide and copper sulfide can also be adopted.
Preferably, the metal sulfide mercury removing agent is obtained by modifying and treating natural sulfur-containing minerals.
Preferably, the metal sulfide mercury removing agent is obtained by artificial synthesis through a method of adding a surfactant; the surfactant is one or a combination of dodecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, potassium monododecyl phosphate, octadecyl amide methyl pyridine chloride or hydrazine.
Preferably, the metal sulfide mercury removing agent can be obtained by loading a metal sulfide on a carrier; the carrier is Fe2O3、Fe3O4、Al2O3One or a combination of molecular sieve, silicon dioxide, silicate, fly ash, zeolite, activated carbon or red mud.
Preferably, the metal sulfide mercury removing agent is sprayed in a spraying mode before the flue gas washing device or the wet dust removal device, or is directly added into a circulating washing liquid of the flue gas washing device or the wet dust removal device, and the metal sulfide mercury removing agent is suspended in water to form a uniform suspension after being added.
Preferably, the flue gas washing device or the wet dust removal device is selected from one or a combination of washing demercuration towers, dynamic wave efficient washers, packed tower washers, venturi washers, spray washers, cyclone atomization chambers, water film dust removers, foam dust removers, orifice washers, impact washers, packed bed washers, air cooling towers and the like.
Preferably, the temperature of the washing liquid or the dedusting liquid in the flue gas washing device or the wet dedusting device is 20-95 ℃, and the ratio of the addition amount of the metal sulfide to the volume of the washing liquid or the dedusting liquid is 0.1-100kg/m3The washing liquid or dedusting liquid is acidic and neutral, wherein the acidity range is c (H)+)=10-7-15mol/L。
In the invention, a gas-liquid interface is generated in a flue gas washing device or a wet dust removal device, and the flue gas is fully contacted with the metal sulfide mercury removal agent suspension liquid, so that at least one of the following is caused:
① gaseous elemental mercury (Hg) in the flue gas0) Or mercury in an oxidized state (Hg)2+) Metal sulphiding adsorbed in the suspension
On the surface of the mercury removing agent;
② oxidized mercury (Hg) in the flue gas2+) Or particulate mercury (Hg)P) And then enters washing liquid or dedusting liquid.
The metal sulfide mercury removing agent has good mechanical property and water resistance, strong hydrophobic capability, and water can remove gaseous elemental mercury (Hg)0) Or mercury in an oxidized state (Hg)2+) The contact effect with the metal sulfide mercury removing agent in the suspension is small, and the gaseous elementary mercury (Hg) is0) Or mercury in an oxidized state (Hg)2+) Can be fully contacted with the surface of the metal sulfide adsorbent and finally captured by the metal sulfide adsorbent. On the one hand, according to the gas absorption double membrane theory, the absorption resistance is mainly in the liquid membrane, the oxidized mercury (Hg) in solution2+) Is captured by adsorbent, and Hg in liquid phase2+The concentration is obviously reduced, and Hg in a liquid film2+The concentration gradient is increased, which will enhance the solution to Hg0Absorption of (2). On the other hand, the solubility product constant of HgS is much smaller than that of metal sulfide, which can react with Hg in solution2+Ion exchange occurs to generate difficultly soluble HgS, and Hg of liquid phase main body is reduced2+Concentration, promoting solution to Hg0Increased absorption of gaseous elemental mercury (Hg)0) The contact probability with the surface of the metal sulfide mercury removing agent is further improved, the mercury removing efficiency is further improved, and the gaseous elementary mercury (Hg) is0) Or mercury in an oxidized state (Hg)2+) Is removed by the metal sulfide mercury removing agent synergistically.
The reaction of the mercury removal process is as follows:
according to the invention, the mercury removing agent is subjected to filter pressing and collection at the bottom flow of the circulating tank of the washing device or the wet dust removal device, mercury in the mercury removing agent is recovered by adopting heat treatment, the composition of the mercury removing agent is similar to that of a smelting raw material, the mercury removing agent after mercury recovery can be used as a metallurgical raw material to enter a smelting process, and the economic benefit and the environmental benefit are high.
Compared with the prior art, the invention has the following advantages:
(1) the metal sulfide mercury removing agent has high mercury removing efficiency, good mechanical property, stable chemical property, low solubility and simple operation
The raw materials are easily obtained, and the cost is low.
(2) The metal sulfide mercury removing agent is less affected by moisture and smoke components, and has acid resistance, water resistance and SO resistance2Has excellent performance, can be used in washing equipment or wet dust removal equipment, and is suitable for high SO2The smelting flue gas purification system can be used for a plurality of parts for flue gas treatment, has wide application range in a flue gas mercury removal system, can utilize the existing flue gas purification equipment, does not change the production process and the existing pollutant control system, and has lower investment cost.
(3) The metal sulfide mercury removing agent can be efficiently combined with mercury in gas and liquid phases to realize Hg0High-efficient desorption has simplified flue gas demercuration system.
(4) The metal sulfide mercury removing agent and mercury form an extremely stable compound (mercury sulfide, HgS), so that high-selectivity fixation of mercury is realized, and the re-release of mercury is avoided.
(5) The invention can recover mercury in the mercury removing agent by the heat treatment method, and the mercury removing agent after mercury recovery can be used as a metallurgical raw material because the components of the mercury removing agent are similar to those of the smelting raw material, so that the economic benefit and the environmental benefit are high.
Detailed Description
The technical solution of the present invention is further described by the following specific examples. The examples are not intended to limit the scope of protection.
Example 1
The metal sulfide mercury removing agent 1 is prepared by a hydrothermal method in the presence of hexadecyl trimethyl ammonium bromide by taking equimolar amounts of ammonium sulfide and copper chloride as reactants, and the specific surface area of the mercury removing agent 1 is 34.3m2(ii) in terms of/g. Adding the metal sulfide mercury removal agent into a simulated flue gas washing device, wherein the set temperature of the washing liquid is 25 ℃, and the ratio of the addition amount of the metal sulfide mercury removal agent to the washing liquid is 1kg/m3The pH of the simulated wash = 2. The VM-3000 mercury-measuring instrument is used for measuring the mercury concentration in real time, and the mass flow meter is accurately controlledThe gas flow of each component is prepared to simulate the components of the smoke, the total gas flow is 1L/min, and the initial Hg is0The concentration is 100 +/-1 mu g/m3In pure N2Under the atmosphere, within 10h, the mercury removing agent of the metal sulfide is used for removing Hg0The removal efficiency was 99.2%.
Example 2
The metal sulfide mercury removing agent 2 is prepared by taking ammonium sulfide, ferric chloride and cupric chloride with the molar ratio of 2:1:1 as reactants and adopting a simple precipitation method in the presence of dodecyl dimethyl benzyl ammonium bromide, and the specific surface area of the mercury removing agent 2 is 20.3m2(ii) in terms of/g. Adding the metal sulfide mercury removal agent into a simulated flue gas washing device, wherein the set temperature of the washing liquid is 25 ℃, and the ratio of the addition amount of the metal sulfide mercury removal agent to the washing liquid is 1kg/m3pH =7 of the simulated wash. The VM-3000 mercury-measuring instrument is used for measuring the mercury concentration in real time, the mass flow meter accurately controls the gas flow of each component to simulate the components of the flue gas, the total gas flow is 1L/min, and the initial Hg is0Concentration of 100. + -. 1. mu.g/m 3 in pure N2Under the atmosphere, within 10h, the mercury removing agent of the metal sulfide is used for removing Hg0The removal efficiency was 95.7%.
Example 3
The ammonium sulfide and the copper chloride with the molar ratio of 1:1 are taken as reactants, the metal sulfide mercury removing agent 3 is prepared by a titration method, and the specific surface area of the mercury removing agent 3 is 5.77m2(ii) in terms of/g. Adding the metal sulfide mercury removal agent into a simulated flue gas washing device, wherein the set temperature of the washing liquid is 25 ℃, and the ratio of the addition amount of the metal sulfide mercury removal agent to the washing liquid is 5kg/m3The pH of the simulated wash = 2. The VM-3000 mercury-measuring instrument is used for measuring the mercury concentration in real time, the mass flow meter accurately controls the gas flow of each component to simulate the components of the flue gas, the total gas flow is 1L/min, and the initial Hg is0The concentration is 100 +/-1 mu g/m3In pure N2Under the atmosphere, within 10h, the mercury removing agent of the metal sulfide is used for removing Hg0The removal efficiency was 85.2%.
Example 4
Adding the metal sulfide mercury removal agent 1 into a simulated flue gas washing device, wherein the set temperature of the washing liquid is 50 ℃, and the addition amount of the metal sulfide mercury removal agent and the washing liquid areThe ratio is 3kg/m3Simulation of c (H) in Wash solution+) And (5) =15 mol/L. The VM-3000 mercury-measuring instrument is used for measuring the mercury concentration in real time, the mass flow meter accurately controls the gas flow of each component to simulate the components of the flue gas, the total gas flow is 1L/min, and the initial Hg is0The concentration is 2000 +/-10 mu g/m3In pure N2Under the atmosphere, in 4h, the mercury removing agent of metal sulfide is used for removing Hg0The removal efficiency is 82.2 percent, and the simulated flue gas atmosphere is 2000ppm SO2、5%O2The carrier gas is N2In 4h, the metal sulfide adsorbent is used for adsorbing Hg0The average removal efficiency was 81.3%.
Example 5
Adding the metal sulfide mercury removal agent 1 into a simulated flue gas washing device, wherein the set temperature of the washing liquid is 25 ℃, and the ratio of the addition amount of the metal sulfide mercury removal agent to the washing liquid is 5kg/m3And the washing liquid uses an actual smelting flue gas washing liquid, and the pH of the washing liquid is = 1.7. The VM-3000 mercury-measuring instrument is used for measuring the mercury concentration in real time, the mass flow meter accurately controls the gas flow of each component to simulate the components of the flue gas, the total gas flow is 1L/min, and the initial Hg is0The concentration is 1000 +/-5 mu g/m3In pure N2Under the atmosphere, after 10h, the metal sulfide mercury removing agent is used for removing Hg0The removal efficiency was 94.3%. In a simulated flue gas atmosphere of 2000ppm SO2、5%O2The carrier gas is N2In 4h, the metal sulfide adsorbent is used for adsorbing Hg0The average demercuration efficiency was 92.3%.
Example 6
Selecting a small amount of natural copper sulfide concentrate, drying the natural copper sulfide concentrate for 12 hours in vacuum at 120 ℃, crushing and screening the dried concentrate, carrying out selenylation modification treatment by adopting an anion exchange method to obtain modified copper sulfide concentrate, and taking a certain amount of modified copper sulfide concentrate ore powder for experiment. Adding the modified copper sulfide concentrate ore powder into a simulated flue gas washing device, wherein the set temperature of washing liquid is 25 ℃, and the ratio of the addition amount of the modified copper sulfide concentrate to the washing liquid is 2kg/m3pH =7 of the simulated wash. The VM-3000 mercury-measuring instrument is used for measuring the mercury concentration in real time, and the mass flow meter accurately controls the gas flow of each component to simulate the components and gas of the flue gasTotal flow 1L/min, initial Hg0Concentration of 100. + -. 1. mu.g/m 3 in pure N2Under the atmosphere, within 10h, the mercury removing agent of the metal sulfide is used for removing Hg0The removal efficiency is higher than 93.8%.
Comparative example 1
Selecting a small amount of natural copper sulfide concentrate, drying the natural copper sulfide concentrate for 12 hours at 120 ℃, crushing and screening the dried concentrate, and taking a certain amount of natural copper sulfide concentrate ore powder for experiment. Adding natural copper sulfide concentrate ore powder into a simulated flue gas washing device, wherein the set temperature of washing liquid is 25 ℃, and the ratio of the addition amount of the natural copper sulfide concentrate to the washing liquid is 2kg/m3pH =7 of the simulated wash. The VM-3000 mercury-measuring instrument is used for measuring the mercury concentration in real time, the mass flow meter accurately controls the gas flow of each component to simulate the components of the flue gas, the total gas flow is 1L/min, and the initial Hg is0The concentration is 100 +/-1 mu g/m3In pure N2Under the atmosphere, within 10h, the mercury removing agent of the metal sulfide is used for removing Hg0The removal efficiency is higher than 32.3%.
Example 8
Respectively taking 3-5mm of alumina globules and sodium X-type zeolite as carriers, taking copper sulfate, ammonium sulfide and the like as raw materials, and preparing the metal sulfide mercury removal agent loaded on the carriers by adding the carriers, soaking, ultrasonic treatment, filtering and drying. Adding the metal sulfide loaded mercury removal agent into a simulated flue gas washing device, wherein the set temperature of the washing liquid is 95 ℃, and the ratio of the addition amount of the metal sulfide loaded mercury removal agent to the washing liquid is 10kg/m3pH =7 of the simulated wash. The VM-3000 mercury-measuring instrument is used for measuring the mercury concentration in real time, the mass flow meter accurately controls the gas flow of each component to simulate the components of the flue gas, the total gas flow is 1L/min, and the initial Hg is0The concentration is 200 +/-2 mu g/m3In pure N2Under the atmosphere, after 4h, the alumina type metal sulfide is loaded with mercury removing agent to Hg0The removal efficiency is 95.2 percent, and the zeolite type metal sulfide loads mercury removal agent to Hg0The removal efficiency was 93.2%.
Example 9
The metallic sulfide mercury removing agent 1 is adopted to carry out experiments in a certain small-sized zinc smelting plant for carrying out a zinc smelting process, and zincThe smelting amount is 8 t/h, and the flue gas amount is 20000 m3H Hg behind the Electrostatic precipitator0The discharge amount is 3.5mg/m3Injecting the metal sulfide mercury removing agent into a two-stage flue gas washing device (dynamic wave washer), wherein the addition amount of the metal sulfide mercury removing agent is 15kg/m3，Hg0The removal efficiency of the catalyst reaches 99.9 percent.
The above embodiments are illustrative of the present invention, and are not intended to limit the present invention, and any modifications of the present invention are within the scope of the present invention.
Claims (9)
1. An application of metal sulfide mercury removing agent in washing and removing mercury in flue gas.
2. The application according to claim 1, characterized in that the application method is as follows: forming metal sulfide mercury removing agent into suspension in a washing device or a wet dust removal device, and removing Hg in flue gas0Conversion to stabilized mercury sulfide to realize Hg0And (4) washing and removing.
3. Use according to claim 2, characterized in that the metal sulphide mercury removing agent is selected from the group consisting of copper sulphide, molybdenum sulphide, sulphur
One or more of zinc sulfide, lead sulfide, manganese sulfide or iron copper sulfide.
4. Use according to claim 1, characterized in that the metal sulphide mercury removing agent is obtained by modification treatment of a natural sulphur-containing mineral.
5. The use according to claim 1, characterized in that the metal sulfide mercury removal agent is obtained by artificial synthesis by means of adding a surfactant; the surfactant is one or a combination of dodecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, potassium monododecyl phosphate, octadecyl amide methyl pyridine chloride or hydrazine.
6. Use according to claim 1, characterized in that the metal sulphide mercury removing agent is obtained by loading a metal sulphide on a support; the carrier is Fe2O3、Fe3O4、Al2O3One or a combination of molecular sieve, silicon dioxide, silicate, fly ash, zeolite, activated carbon or red mud.
7. The use according to claim 1, wherein the metal sulfide mercury removing agent is sprayed in a spraying manner before the flue gas scrubbing device or the wet dust removal device, or is directly added into the circulating scrubbing liquid of the flue gas scrubbing device or the wet dust removal device, and the metal sulfide mercury removing agent is suspended in water after being added to form a uniform suspension.
8. The use according to claim 7, wherein the flue gas scrubbing device or wet dust removal device is selected from one or a combination of a scrubber demercuration tower, a dynamic wave high efficiency scrubber, a packed tower scrubber, a venturi scrubber, a spray scrubber, a cyclone atomization chamber, a water film dust scrubber, a foam dust scrubber, an orifice scrubber, an impingement scrubber, a packed bed scrubber, an air cooling tower device.
9. The use according to claim 8, wherein the temperature of the scrubbing or dedusting liquid in the flue gas scrubbing or wet dedusting apparatus is 20-95 ℃, and the ratio of the addition amount of the metal sulfide mercury removal agent to the volume of the scrubbing or dedusting liquid is 0.1-100g/m3The washing liquid or dedusting liquid is acidic and neutral, wherein the acidity range is c (H)+)=10-7-15mol/L。
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| CN112934197A (en) * | 2021-02-01 | 2021-06-11 | 中南大学 | Macroporous skeleton hydrophobic demercuration material, preparation method and application thereof |
| CN113501574A (en) * | 2021-07-13 | 2021-10-15 | 中南大学 | Method for resource utilization of industrial copper-containing wastewater |
| CN115318258A (en) * | 2022-06-27 | 2022-11-11 | 中南大学 | Metal sulfide adsorbent based on mechanical ball milling and preparation method and application thereof |
| WO2023035587A1 (en) * | 2021-09-13 | 2023-03-16 | 昆明理工大学 | Method for removing impurity mercury from crude selenium |
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| CN112023665A (en) * | 2020-08-31 | 2020-12-04 | 中南大学 | Method for purifying elemental mercury in flue gas by using nano copper sulfide hydrosol wet method |
| CN112023665B (en) * | 2020-08-31 | 2021-06-25 | 中南大学 | Method for purifying elemental mercury in flue gas by using nano copper sulfide hydrosol wet method |
| CN112755764A (en) * | 2020-12-16 | 2021-05-07 | 中南大学 | Stable suspension system for removing mercury in flue gas and recovery method thereof |
| CN112755764B (en) * | 2020-12-16 | 2021-10-19 | 中南大学 | Stable suspension system for removing mercury in flue gas and recovery method thereof |
| CN112934197A (en) * | 2021-02-01 | 2021-06-11 | 中南大学 | Macroporous skeleton hydrophobic demercuration material, preparation method and application thereof |
| CN113501574A (en) * | 2021-07-13 | 2021-10-15 | 中南大学 | Method for resource utilization of industrial copper-containing wastewater |
| WO2023035587A1 (en) * | 2021-09-13 | 2023-03-16 | 昆明理工大学 | Method for removing impurity mercury from crude selenium |
| CN115318258A (en) * | 2022-06-27 | 2022-11-11 | 中南大学 | Metal sulfide adsorbent based on mechanical ball milling and preparation method and application thereof |
| CN115318258B (en) * | 2022-06-27 | 2023-10-27 | 中南大学 | Metal sulfide adsorbent based on mechanical ball milling and preparation method and application thereof |
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