CN114100576A - Cobalt disulfide/carbon composite material and preparation method and application thereof - Google Patents

Cobalt disulfide/carbon composite material and preparation method and application thereof Download PDF

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CN114100576A
CN114100576A CN202111403028.6A CN202111403028A CN114100576A CN 114100576 A CN114100576 A CN 114100576A CN 202111403028 A CN202111403028 A CN 202111403028A CN 114100576 A CN114100576 A CN 114100576A
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cobalt
composite material
carbon composite
disulfide
cobalt disulfide
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CN114100576B (en
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刘恢
李焌源
沈锋华
何书丹
向开松
刘操
李超芳
闵小波
林璋
李青竹
柴立元
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Central South University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/025—Other waste gases from metallurgy plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2258/00—Sources of waste gases
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    • B01D2258/0283—Flue gases

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Abstract

The invention discloses a cobalt disulfide/carbon composite material and a preparation method and application thereof. Placing the porous carbon material in a cobalt salt solution for dipping, and then adding a sulfur source solution for carrying out a vulcanization reaction to obtain a vulcanization reaction solution; transferring the vulcanization reaction liquid into a high-pressure reaction kettle for hydrothermal reaction to obtain a precursor material; and carrying out heat treatment on the precursor material under the condition of oxygen isolation to obtain the cobalt disulfide/carbon composite material. The composite material has good stability, more active sites for absorbing elemental mercury, high activity and good tolerance to sulfur dioxide, is particularly suitable for removing the elemental mercury in the colored smelting flue gas containing high-concentration sulfur dioxide, and the preparation method has the advantages of simple operation, short flow and mild conditions, and is beneficial to large-scale production.

Description

Cobalt disulfide/carbon composite material and preparation method and application thereof
Technical Field
The invention relates to a mercury adsorption material, in particular to a cobalt disulfide/carbon composite material, a preparation method thereof and application of the cobalt disulfide/carbon composite material as a simple substance mercury adsorption material, and belongs to the technical field of flue gas pollutant control.
Background
The nonferrous metal metallurgy is the second largest mercury emission source next to coal burning, and compared with coal burning flue gas, SO in nonferrous metal smelting flue gas2The concentration is very high (0.5% -15%), which is one of the main difficulties faced in the demercuration of colored flue gas. The mercury in flue gas has three forms, granular mercury (Hg)p) Mercury (Hg) in its oxidized state2+) And elemental mercury (Hg)0)。 HgpAnd Hg2+And respectively adopting a traditional dust removal device and a wet washing device to remove. And Hg0The water solubility is low, the chemical inertness is high, the volatilization is easy, the traditional process is difficult to remove, and a special demercuration technology needs to be developed.
At present, the control of the elemental mercury in the nonferrous smelting industry mainly adopts the Swedish Boleton technology and utilizes the highly toxic HgCl2Absorbing flue gas mercury to obtain calomel, but the technology is used for absorbing high-concentration SO2The operation is unstable under the condition, the investment cost is high, and the operation and maintenance are complex.
At present, the most promising flue gas mercury recovery technology is to adopt an adsorbent to adsorb and recover mercury. Some typical sorbent adsorption mercury recovery schemes have been disclosed in the prior art. For example: chinese patent (CN109529885A) discloses a Co9S8The biomass charcoal composite material is prepared by loading cobalt and sulfur on the surface of biomass simultaneously, and then calcining at high temperature to carbonize the biomass and obtain Co9S8The adsorbent has better demercuration performance under the conditions of high sulfur and high chlorine, but the demercuration efficiency of the adsorbent under nitrogen is very low, namely the demercuration activity of the adsorbent is very poor, and the adsorbent is seriously dependent on HCl in flue gas to promote mercury adsorption; chinese patent (CN109092239A) discloses a CoxZn(1-x)The S mercury removing agent is obtained by high-temperature hydrothermal co-vulcanization of cobalt salt and zinc salt, the adsorbent solves the problem of weak adsorption capacity of zinc mercury sulfide, but the synthesis process of the adsorbent comprises conditions of high-temperature hydrothermal, low solid-liquid ratio, high cobalt content and the like, so that the cost of the adsorbent is higher. The existing scheme has better mercury removal capability under specific conditions, but still needs to be further improved in the aspects of high-sulfur chlorine-free flue gas application, adsorbent production cost and the like. Accordingly, there is a need in the art for further research and improvement to better meet the complex demands of flue gas mercury removal for modern nonferrous smelting enterprises.
Disclosure of Invention
Aiming at the problems in the prior art, the first purpose of the invention is to provide a cobalt disulfide/carbon composite material formed by loading nano cobalt disulfide on the surface of porous carbon, wherein the composite material has good stability, a plurality of sites for adsorbing elemental mercury and high activity.
The second purpose of the invention is to provide a preparation method of the cobalt disulfide/carbon composite material, which has the advantages of simple operation, mild condition and low cost and is beneficial to large-scale production.
The third purpose of the invention is to provide an application of the cobalt disulfide/carbon composite material as a simple substance mercury adsorption material, which has high removal efficiency of the simple substance mercury, stable demercuration performance under chlorine-free flue gas, can keep higher demercuration activity for a long time, has good tolerance to sulfur dioxide, and is particularly suitable for demercuration of nonferrous smelting flue gas.
In order to achieve the technical purpose, the invention provides a preparation method of a cobalt disulfide/carbon composite material, which comprises the following steps:
1) placing the porous carbon material in a cobalt salt solution for dipping, and then adding a sulfur source solution for carrying out a vulcanization reaction to obtain a vulcanization reaction solution;
2) transferring the vulcanization reaction liquid into a high-pressure reaction kettle for hydrothermal reaction to obtain a precursor material;
3) and carrying out heat treatment on the precursor material under the condition of oxygen isolation to obtain the material.
The key point of the technical scheme is that an excessive sulfur source is added at one time, and the step-by-step ordered and efficient vulcanization of cobalt is realized through three vulcanization processes of heating vulcanization, hydrothermal vulcanization and high-temperature vulcanization, so that the stable combination and the dispersed loading of cobalt sulfide on the surface of a porous carbon material are realized, the crystal structure and the crystallinity of cobalt disulfide are orderly regulated and controlled, the nano cobalt disulfide particles with higher activity are obtained, and the adsorption activity of elemental mercury is greatly improved.
Preferably, the concentration of the cobalt salt solution is 0.003-1.5 mol/L. The concentration of the cobalt salt solution is more preferably 0.1 to 1 mol/L.
Preferably, the molar ratio of the porous carbon material to the cobalt salt in the cobalt salt solution is 20-450: 1.
Preferably, the molar ratio of the sulfur source in the sulfur source solution to the cobalt salt in the cobalt salt solution is 2-4: 1. By adopting a proper excessive sulfur source, cobalt ions can be fully converted into cobalt disulfide, and meanwhile, excessive sulfur can participate in the subsequent high-temperature reaction process so as to improve the stability of the composite material.
As a preferable scheme, the porous carbon material is at least one of porous carbon spheres, porous carbon fibers, porous carbon rods and amorphous porous carbon. The preferred porous carbon material has a higher specific surface area, and can improve the dispersibility of the supported cobalt disulfide.
As a preferable scheme, the cobalt salt is a common water-soluble cobalt salt, and specifically, cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt oxalate and the like.
As a preferable embodiment, the sulfur source is a water-soluble sulfur-containing compound, such as sodium sulfide, thiourea, sodium thiosulfate, etc.
As a preferred embodiment, the impregnation conditions are: the temperature is 20-80 ℃ and the time is 10-120 min. The impregnation process mainly utilizes the high specific surface area of the porous carbon to adsorb cobalt ions, thereby being beneficial to the in-situ deposition of the subsequent cobalt disulfide in the porous carbon material.
As a preferred embodiment, the conditions of the sulfurization reaction are: the temperature is 20-80 ℃ and the time is 10-120 min. The primary sulfurization deposition of cobalt ions is mainly realized through the sulfurization reaction process, so that cobalt is deposited on the surface of the porous carbon material framework in situ in the form of cobalt sulfide.
As a preferred embodiment, the hydrothermal reaction conditions are: the temperature is 60-150 ℃, and the time is 2-20 h. The preferable hydrothermal reaction temperature is 80-120 ℃. The preferable hydrothermal reaction time is 5 to 10 hours. The reaction temperature in the hydrothermal reaction process is relatively low, and the further vulcanization of cobalt is mainly realized on the basis of the vulcanization reaction, so that the in-situ compounding degree of cobalt disulfide on the surface of the porous carbon material is improved.
As a preferable mode, the heat treatment conditions are: the temperature is 250-600 ℃, and the time is 1-5 h. The preferable heat treatment temperature is 300-500 ℃, and the preferable heat treatment time is 1-3 hours. The method is important for forming the composite material through the heat treatment process, on one hand, the cobalt can be further thoroughly vulcanized, on the other hand, the crystal structure of the cobalt disulfide can be effectively regulated, so that amorphous cobalt disulfide with low crystallinity is converted into nano cobalt disulfide crystals with high crystallinity and order at high temperature, the activity of the cobalt disulfide combined with elemental mercury is greatly improved, in addition, under the action of high temperature, part of excessive sulfur can form sulfur bridging between porous carbon and cobalt disulfide, so that the nano cobalt disulfide can be stably combined on the surface of the porous carbon material, the structural stability and the activity of the material are increased, meanwhile, under the action of high temperature, redundant elemental sulfur in the porous carbon is sublimated, the surface area of the composite material can be increased, the mass transfer rate with mercury is increased, and the mercury removal efficiency is improved. The heat treatment is performed under a protective atmosphere such as nitrogen, an inert gas, and the like, specifically at least one of nitrogen, argon, and helium.
The invention also provides a cobalt disulfide/carbon composite material, which is prepared by the preparation method.
As a preferable scheme, the material is formed by loading nano cobalt disulfide on the surface of porous carbon; wherein, the mass percentage content of the nano cobalt disulfide is 5 to 50 percent.
The invention also provides an application of the cobalt disulfide/carbon composite material, which is used as an elemental mercury adsorption material.
The cobalt disulfide/carbon composite material provided by the invention comprises the following specific steps:
(1) dipping: adding a porous carbon material into a cobalt salt solution, mixing and stirring, wherein the impregnation temperature is 20-80 ℃, and the impregnation time is 10-120 min, so as to obtain an impregnation liquid; the concentration of the cobalt salt solution is 0.003-1 mol/L, and the molar ratio of the porous carbon material to the cobalt salt is 20-450: 1;
(2) and (3) vulcanization: adding a sulfur source solution into the impregnation solution, mixing and stirring, wherein the vulcanization temperature is 20-80 ℃, and the vulcanization time is 10-120 min to obtain a vulcanization solution; the molar ratio of the sulfur source to the cobalt salt is 2-4: 1;
(3) hydrothermal: carrying out hydrothermal reaction on the vulcanizing liquid, wherein the hydrothermal temperature is 60-150 ℃, and the hydrothermal time is 2-20 h, so as to obtain a hydrothermal solution;
(4) and (3) drying: cooling the hydrothermal solution to 20-50 ℃, filtering, and drying the filtered product at 60-120 ℃ to obtain a precursor;
(5) surface heat treatment: and heating the precursor under a protective atmosphere to carry out surface heat treatment at the temperature of 250-600 ℃ for 1-5 h, and naturally cooling to obtain the cobalt disulfide/carbon composite material.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the cobalt disulfide/carbon composite material provided by the invention is formed by stably dispersing and loading nano cobalt disulfide particles on the surface of porous carbon, has high specific surface, good stability and high activity of adsorbing elemental mercury, and can be widely applied as an elemental mercury adsorbing material.
The preparation method of the cobalt disulfide/carbon composite material provided by the invention is simple to operate, mild in condition, low in cost and beneficial to large-scale production.
The cobalt disulfide/carbon composite material provided by the invention can be used as a simple substance mercury adsorption material, has high removal efficiency on simple substance mercury, stable demercuration performance, can keep higher demercuration activity for a long time, has good tolerance to sulfur dioxide, and is particularly suitable for demercuration of smelting flue gas.
Drawings
FIG. 1 is a schematic view of a process flow for preparing a cobalt disulfide/carbon composite material according to the present invention.
Fig. 2 is an XRD pattern of the cobalt disulfide/carbon composite precursor and the cobalt disulfide/carbon composite prepared in example 4 of the present invention.
Figure 3 is an SEM image of cobalt disulfide/carbon composite prepared in example 4 of the present invention.
FIG. 4 is a graph showing the results of a long-time demercuration test of the cobalt disulfide/carbon composite material prepared in example 4 of the present invention; (demercuration material 10mg, mercury concentration 200 mug/m)3Total gas flow 600mL/min, SO2 6％、O2 6％)。
Detailed Description
The following specific examples are illustrative of the preferred embodiments, and it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the embodiments of the invention and are intended to be within the scope of the embodiments of the invention.
The present invention will be further described with reference to a plurality of examples, but the scope of the claims of the present invention is not limited to the following specific examples, and can be modified and implemented as appropriate within the scope not changing the main claims.
The following examples adopt a packed column to perform demercuration performance tests, 100mg of cobalt disulfide/carbon composite material is weighed and put into a packed column with the inner diameter of 10mm, mercury adsorption treatment is performed at 60 ℃, the flow rate of mercury-containing flue gas is 600mL/min, and the flue gas component is SO26% (volume percent))、O26% (volume percentage) of mercury with a concentration of Hg0200μg/m3And a mercury analyzer is adopted to monitor the change of the mercury concentration on line.
Example 1
Preparing 1L of cobalt nitrate solution with the concentration of 0.1mol/L, preparing 1L of thiourea solution with the concentration of 0.25mol/L, and weighing 250g of porous carbon spheres. Adding a cobalt nitrate solution into a high-pressure reaction kettle, heating to 60 ℃, adding porous carbon balls into the cobalt nitrate solution, stirring for 30min for impregnation, then adding a thiourea solution, stirring for 100min for vulcanization, then sealing the reaction kettle, heating to 100 ℃, stirring at a constant temperature for 10h, naturally cooling to 50 ℃, discharging, filtering, drying at 80 ℃ for 12h to obtain a cobalt disulfide/carbon composite material precursor, then placing the precursor into a tube furnace, heating to 300 ℃ under an argon atmosphere, preserving heat for 2h, and naturally cooling to obtain the cobalt disulfide/carbon composite material. The obtained cobalt disulfide/carbon composite material is subjected to mercury removal performance test, and the mercury removal efficiency reaches more than 96% in 30 minutes.
Example 2
Preparing 1L of cobalt nitrate solution with the concentration of 0.2mol/L, preparing 1L of thiourea solution with the concentration of 0.6mol/L, and weighing 250g of porous carbon spheres. Adding a cobalt nitrate solution into a high-pressure reaction kettle, heating to 30 ℃, adding porous carbon balls into the cobalt nitrate solution, stirring for 10min for impregnation, then adding a thiourea solution, stirring for 30min for vulcanization, then sealing the reaction kettle, heating to 120 ℃, stirring at a constant temperature for 5h, naturally cooling to 50 ℃, discharging, filtering, drying at 80 ℃ for 12h to obtain a cobalt disulfide/carbon composite material precursor, then placing the precursor into a tube furnace, heating to 500 ℃ under an argon atmosphere, preserving heat for 1h, and naturally cooling to obtain the cobalt disulfide/carbon composite material. The obtained cobalt disulfide/carbon composite material is subjected to mercury removal performance test, and the mercury removal efficiency reaches more than 98% in 30 minutes.
Example 3
Preparing 1L of cobalt sulfate solution with the concentration of 0.4mol/L, preparing 1L of thiourea solution with the concentration of 1mol/L, and weighing 250g of coconut charcoal. Adding a cobalt sulfate solution into a high-pressure reaction kettle, heating to 30 ℃, adding coconut shell carbon into a cobalt nitrate solution, stirring for 20min for impregnation, then adding a thiourea solution, stirring for 60min for vulcanization, then sealing the reaction kettle, heating to 150 ℃, stirring at constant temperature for 5h, naturally cooling to 50 ℃, discharging, filtering, drying at 80 ℃ for 12h to obtain a cobalt disulfide/carbon composite material precursor, then placing the precursor into a tubular furnace, heating to 400 ℃ under an argon atmosphere, preserving heat for 1h, and naturally cooling to obtain the cobalt disulfide/carbon composite material. The obtained cobalt disulfide/carbon composite material is subjected to mercury removal performance test, and the mercury removal efficiency reaches more than 98% in 30 minutes.
Example 4
Preparing 1L of cobalt chloride solution with the concentration of 0.5mol/L, preparing 1L of thiourea solution with the concentration of 1.2mol/L, and weighing 125g of porous carbon fiber. Adding a cobalt chloride solution into a high-pressure reaction kettle, heating to 60 ℃, adding porous carbon fibers into a cobalt nitrate solution, stirring for 30min for impregnation, then adding a thiourea solution, stirring for 120min for vulcanization, then sealing the reaction kettle, heating to 80 ℃, stirring at a constant temperature for 8h, naturally cooling to 50 ℃, discharging, filtering, drying at 80 ℃ for 8h to obtain a cobalt disulfide/carbon composite material precursor, then placing the precursor into a tubular furnace, heating to 300 ℃ under an argon atmosphere, preserving heat for 1.5h, and naturally cooling to obtain the cobalt disulfide/carbon composite material. The obtained cobalt disulfide/carbon composite material is subjected to mercury removal performance test, and the mercury removal efficiency reaches more than 98% in 30 minutes.
XRD analysis was performed on the cobalt disulfide/carbon composite precursor (80 ℃) and the cobalt disulfide/carbon composite (80-300 ℃) in example 4, and the results are shown in fig. 2, in which cobalt in the cobalt disulfide/carbon composite precursor and the cobalt disulfide/carbon composite mainly exists in the form of cobalt disulfide, and after heat treatment, the crystallinity of cobalt disulfide becomes high.
SEM analysis of the cobalt disulfide/carbon composite (80-300 ℃) of example 4 is shown in FIG. 3. The carbon material exists in the form of porous carbon spheres, and the cobalt disulfide is attached to the surfaces of the porous carbon spheres in a granular form. The form endows the cobalt disulfide/carbon composite material with more mercury-absorbing active sites, the contact channel is shorter, and the mercury-absorbing and mercury-desorbing speeds can be greatly improved.
The cobalt disulfide/carbon composite (80-300 c) of example 4 was subjected to a long-term mercury removal test, the results of which are shown in figure 4. The demercuration efficiency is kept above 98% in 120 minutes, and after 10 hours, the demercuration efficiency is over 80%. Indicating that the mercury removal catalyst has good long-term mercury removal stability.
Example 5
Preparing 1L of cobalt nitrate solution with the concentration of 1.2mol/L, preparing 1L of sodium sulfide solution with the concentration of 3mol/L, and weighing 1000g of coconut shell carbon. Adding a cobalt nitrate solution into a high-pressure reaction kettle, heating to 50 ℃, adding coconut shell carbon into the cobalt nitrate solution, stirring for 30min for impregnation, then adding a sodium sulfide solution, stirring for 60min for vulcanization, then sealing the reaction kettle, heating to 150 ℃, stirring at constant temperature for 5h, naturally cooling to 50 ℃, discharging, filtering, drying at 100 ℃ for 12h to obtain a cobalt disulfide/carbon composite material precursor, then placing the precursor into a tubular furnace, heating to 400 ℃ under an argon atmosphere, preserving heat for 1h, and naturally cooling to obtain the cobalt disulfide/carbon composite material. The obtained cobalt disulfide/carbon composite material is subjected to mercury removal performance test, and the mercury removal efficiency reaches more than 98.5% in 30 minutes.
Example 6
Preparing 1L of cobalt chloride solution with the concentration of 0.4mol/L, preparing 1L of thiourea solution with the concentration of 1mol/L, and weighing 250g of coconut shell carbon. Adding a cobalt chloride solution into a high-pressure reaction kettle, heating to 50 ℃, adding coconut shell carbon into a cobalt nitrate solution, stirring for 30min for impregnation, then adding a thiourea solution, stirring for 60min for vulcanization, then sealing the reaction kettle, heating to 120 ℃, stirring at a constant temperature for 5h, naturally cooling to 50 ℃, discharging, filtering, drying at 100 ℃ for 12h to obtain a cobalt disulfide/carbon composite material precursor, then placing the precursor into a tubular furnace, heating to 400 ℃ under an argon atmosphere, preserving heat for 1h, and naturally cooling to obtain the cobalt disulfide/carbon composite material. The obtained cobalt disulfide/carbon composite material is subjected to mercury removal performance test, and the mercury removal efficiency reaches more than 99% in 30 minutes.
Example 7
0.8L of cobalt nitrate solution with the concentration of 1mol/L is prepared, 1L of thiourea solution with the concentration of 2mol/L is prepared, and 1200g of porous carbon spheres are weighed. Adding a cobalt nitrate solution into a high-pressure reaction kettle, heating to 80 ℃, adding an activated carbon ball into the cobalt nitrate solution, stirring for 30min for impregnation, then adding a thiourea solution, stirring for 60min for vulcanization, then heating to 120 ℃ in a sealed reaction kettle, stirring at a constant temperature for 10h, naturally cooling to 50 ℃, discharging, filtering, drying at 100 ℃ for 20h to obtain a cobalt disulfide/carbon composite material precursor, then placing the precursor into a tube furnace, heating to 300 ℃ in an argon atmosphere, preserving heat for 2h, and naturally cooling to obtain the cobalt disulfide/carbon composite material. The obtained cobalt disulfide/carbon composite material is subjected to mercury removal performance test, and the mercury removal efficiency reaches more than 98.8% in 30 minutes.
Example 8 (comparative example)
0.8L of cobalt nitrate solution with the concentration of 1mol/L is prepared, 1L of thiourea solution with the concentration of 2mol/L is prepared, and 1200g of porous carbon spheres are weighed. Adding a cobalt nitrate solution into a high-pressure reaction kettle, heating to 80 ℃, adding an activated carbon ball into the cobalt nitrate solution, stirring for 30min for impregnation, then adding a thiourea solution, stirring for 60min for vulcanization, then sealing the reaction kettle, heating to 120 ℃, stirring at a constant temperature for 10h, naturally cooling to 50 ℃, discharging, filtering, drying at 100 ℃ for 20h to obtain a cobalt disulfide/carbon composite material precursor, and naturally cooling to obtain the cobalt disulfide/carbon composite material. The obtained cobalt disulfide/carbon composite material is subjected to a demercuration performance test, and the demercuration efficiency is close to 60% in 30 minutes.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A preparation method of a cobalt disulfide/carbon composite material is characterized by comprising the following steps: the method comprises the following steps:
1) placing the porous carbon material in a cobalt salt solution for dipping, and then adding a sulfur source solution for carrying out a vulcanization reaction to obtain a vulcanization reaction solution;
2) transferring the vulcanization reaction liquid into a high-pressure reaction kettle for hydrothermal reaction to obtain a precursor material;
3) and carrying out heat treatment on the precursor material under the condition of oxygen isolation to obtain the material.
2. The method for preparing the cobalt disulfide/carbon composite material according to claim 1, wherein:
the concentration of the cobalt salt solution is 0.003-1.5 mol/L;
the mol ratio of the porous carbon material to the cobalt salt in the cobalt salt solution is 20-450: 1;
the molar ratio of the sulfur source in the sulfur source solution to the cobalt salt in the cobalt salt solution is 2-4: 1.
3. The method for preparing the cobalt disulfide/carbon composite material according to claim 2, wherein:
the porous carbon material is at least one of porous carbon balls, porous carbon fibers, porous carbon rods and amorphous porous carbon;
the cobalt salt is at least one of cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt oxalate;
the sulfur source is at least one of sodium sulfide, thiourea and sodium thiosulfate.
4. The method for preparing the cobalt disulfide/carbon composite material according to claim 1, wherein: the impregnation conditions are as follows: the temperature is 20-80 ℃ and the time is 10-120 min.
5. The method for preparing the cobalt disulfide/carbon composite material according to claim 1, wherein: the conditions of the sulfurization reaction are as follows: the temperature is 20-80 ℃ and the time is 10-120 min.
6. The method for preparing the cobalt disulfide/carbon composite material according to claim 1, wherein: the conditions of the hydrothermal reaction are as follows: the temperature is 60-150 ℃, and the time is 2-20 h.
7. The method for preparing the cobalt disulfide/carbon composite material according to claim 1, wherein: the conditions of the heat treatment are as follows: the temperature is 250-600 ℃, and the time is 1-5 h.
8. A cobalt disulfide/carbon composite material is characterized in that: the preparation method of any one of claims 1 to 7.
9. The cobalt disulfide/carbon composite of claim 8, wherein: the nano cobalt disulfide is loaded on the surface of porous carbon; wherein, the mass percentage content of the nano cobalt disulfide is 5 to 50 percent.
10. Use of a cobalt disulphide/carbon composite material according to claim 8 or 9, wherein: the mercury-free mercury adsorption material is applied as an elemental mercury adsorption material.
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CN115108553A (en) * 2022-07-25 2022-09-27 浙江农林大学 Method for preparing nitrogen-doped high-specific-surface-area activated carbon by assisting wood biomass
CN115318210A (en) * 2022-08-11 2022-11-11 宿辉 Preparation method and application of cobalt disulfide/porous carbon/silicon carbide aerogel composite material for electromagnetic shielding

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CN115318210A (en) * 2022-08-11 2022-11-11 宿辉 Preparation method and application of cobalt disulfide/porous carbon/silicon carbide aerogel composite material for electromagnetic shielding
CN115318210B (en) * 2022-08-11 2024-04-02 宿辉 Preparation method and application of cobalt disulfide/porous carbon/silicon carbide aerogel composite material for electromagnetic shielding

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