CN115025748B - Novel copper selenide composite material for mercury removal and preparation method and application thereof - Google Patents
Novel copper selenide composite material for mercury removal and preparation method and application thereof Download PDFInfo
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- CN115025748B CN115025748B CN202210648665.8A CN202210648665A CN115025748B CN 115025748 B CN115025748 B CN 115025748B CN 202210648665 A CN202210648665 A CN 202210648665A CN 115025748 B CN115025748 B CN 115025748B
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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
- B01J20/0203—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
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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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
- B01D53/02—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
- B01D53/04—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 with stationary adsorbents
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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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- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- 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
- B01J20/0251—Compounds of Si, Ge, Sn, Pb
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The application discloses a novel copper selenide composite material for mercury removal and a preparation method and application thereof, wherein the combination of elemental selenium (Se) and mercury is utilized to generate biological antagonism, and the mercury is separated into insoluble and metabolically active mercury selenide; at the same time Fe 2 O 3 The specific surface area and magnetism of particles are increased, active points of mercury are more easily damaged, mercury components are released or exposed, and the mercury removal rate of flue gas of the coal-fired power plant is greatly improved. The method for treating the flue gas of the coal-fired power plant has the advantages that the highest mercury removal rate of the low/medium/high temperature section can reach more than 96%, and compared with the traditional mercury removal process, the method for treating the flue gas of the coal-fired power plant has the advantages of simple operation process, low energy consumption, easiness in industrial scale, high-efficiency mercury removal of the whole temperature section and the like.
Description
Technical Field
The application belongs to the technical field of environmental protection, and particularly relates to a novel copper selenide composite material for mercury removal, and a preparation method and application thereof.
Background
Mercury is a highly toxic heavy metal, and is one of the most dangerous pollutants in the world due to its long-term closed-loop atmospheric transport and bioaccumulation properties. In 2017, the primordial of 128 countries and the first government have signed the "water-mercury convention" aimed at standardizing the emission of mercury from various artificial sources to alleviate serious mercury pollution in modern society. Among them, in artificial mercury emissions, coal burning of coal-fired power plants is considered as the largest source of mercury pollution.
Three forms of mercury have been found in power plant emissions: zero-valent mercury (Hg 0), divalent mercury (hg2+) and particulate mercury (Hgp). Currently, electric precipitators (ESPs), wet Flue Gas Desulfurization (WFGD), and Selective Catalytic Reduction (SCR) can remove Hg < 2+ > and Hgp to a large extent. However, low/medium/high temperature section zero-valent mercury Hg0 is difficult to remove by these devices due to its volatility, insolubility and chemical stability. Thus, the removal of zero-valent mercury from exhaust gas in multiple temperature zones remains an important issue. Many sorbents have been used to capture mercury in flue gases, such as g-C3N4, activated carbon, excess metals, metal sulfides or metal selenides.
The combination of elemental selenium (Se) with mercury produces biological antagonism, so selenium can separate mercury into insoluble and metabolically active mercury selenide. Because selenium is almost insoluble in water, selenide is considered to be one of the materials potentially useful for mercury removal from flue gases in coal-fired power plants. The application discloses a series of novel copper selenide composite materials (CuSe/Fe) synthesized by a room temperature precipitation method and a hydrothermal method 2 O 3 ) And the method is used for removing mercury from the flue gas of the coal-fired power plant with multiple temperature sections, and provides an economic and effective method reference for adsorbing Hg0 in the flue gas of the coal-fired power plant. Compared with the traditional mercury removal process, the method greatly improves the mercury removal rate, realizes the efficient mercury removal of the flue gas of the coal-fired power plant, and has the advantages of simple operation process, low energy consumption, easy industrial scale, high-efficiency mercury removal in the full-temperature section and the like.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
Therefore, the application aims to overcome the defects in the prior art and provide a preparation method of a novel copper selenide composite material for mercury removal.
In order to solve the technical problems, the application provides the following technical scheme: comprising the steps of (a) a step of,
dissolving sodium hydroxide and selenium powder in a diluted hydrazine hydrate solution to obtain a mixed solution A;
copper sulfate is dissolved in deionized water to obtain a mixed solution B;
mixing the solution A and the solution B together, stirring and further aging, and then cleaning with deionized water and absolute ethyl alcohol for three times to obtain a CuSe sample;
sample CuSe and FeCl 3 Adding the mixture into absolute ethyl alcohol and stirring; adding a surfactant, and continuing stirring to obtain a solution C;
heating the solution C in a reaction vessel made of polytetrafluoroethylene, cooling, washing the obtained sample with deionized water and absolute ethanol for three times, and drying to obtain CuSe/Fe 2 O 3 And (3) compounding the product.
As a preferred embodiment of the present application, wherein: the mixed solution A comprises 1.0g of sodium hydroxide, 2.0g of selenium powder and 20ml of diluted hydrazine hydrate solution.
As a preferred embodiment of the present application, wherein: the mixed solution B contains 4.0g of copper sulfate and 40ml of deionized water.
As a preferred embodiment of the present application, wherein: and adding the CuSe sample and FeCl3 into absolute ethyl alcohol for stirring, wherein the addition amount of the FeCl3 is 15-35 wt% based on the mass ratio of the CuSe.
As a preferred embodiment of the present application, wherein: the surfactant was 0.72g sodium acetate dissolved in 10ml deionized water.
As a preferred embodiment of the present application, wherein: the heating is carried out, wherein the heating temperature is 200 ℃, and the heating time is 24 hours.
Another object of the present application is to overcome the deficiencies of the prior art and to provide a novel copper selenide composite for mercury removal.
It is a further object of the present application to overcome the deficiencies of the prior art and to provide the use of a novel copper selenide composite for mercury removal.
In order to solve the technical problems, the application provides the following technical scheme: comprising the steps of (a) a step of,
CuSe/Fe 2 O 3 The composite material is used as an adsorbent to be placed in a mercury vapor generator simulating a waste environment, and a mercury removal evaluation experiment is carried out.
As a preferred embodiment of the present application, wherein: the airflow speed of the mercury vapor generator is regulated to be 1.2L/min, and the carrier gas flow speed is regulated to be 0.2L/min.
As a preferred embodiment of the present application, wherein: the amount of the adsorbent added was 50mg.
The application has the beneficial effects that:
(1) The application prepares CuSe/Fe 2 O 3 The composite material is used as adsorption particles, and the combination of elemental selenium and mercury can generate biological antagonism, so that the selenium can separate the mercury into insoluble and metabolically active mercury selenide. At the same time Fe 2 O 3 The existence of the particles increases the specific surface area and magnetism, and the active points of mercury are more easily damaged, and mercury components are released or exposed, so that the mercury removal rate of the flue gas of the coal-fired power plant can be greatly improved.
(2) Through multiple experiments, the application discovers a key technical inflection point with the best technical effect: when Fe is carried on 2 O 3 When the particle mass is 25wt%, the damage effect on the HgO structure is optimal, and the chemical adsorption force between Hg substances and molecules of the coal-fired flue gas can be damaged to the maximum extent.
(3) Compared with the traditional chemical leaching mercury removal process, the application adopts Fe 2 O 3 The method has the advantages of simple operation process, low energy consumption, high-efficiency mercury removal in a full-temperature section and the like, and has very wide application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is an SEM image of a CF-25 composite product prepared according to example 1 of the present application.
FIG. 2 is an XRD pattern of the CF-25 composite product prepared in example 1 of the present application.
FIG. 3 shows Hg at low temperature for the series of CF samples prepared in examples 1 to 5 of the present application 0 Removal ofPerformance diagram.
FIG. 4 shows the Hg at the medium temperature range for the CF samples prepared in examples 1 to 5 according to the present application 0 The performance map is removed.
FIG. 5 shows Hg at a high temperature range for the CF samples prepared in examples 1 to 5 of the present application 0 The performance map is removed.
FIG. 6 shows the Hg at the low, medium and high temperature ranges for the CF-25 composite product prepared in comparative example 1 of the present application 0 The performance map is removed.
FIG. 7 shows a reaction platform for flue gas mercury adsorption experiments using a fixed bed in accordance with the present application
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
1.0g of sodium hydroxide and 2g of selenium powder are dissolved in 20ml of diluted hydrazine hydrate solution to obtain a mixed solution A; 4.0g of copper sulfate was dissolved in 40ml of deionized water to obtain a mixed solution B;
the mixed solution A, B was mixed and further aged by stirring for 2 hours; taking out the sample, and respectively cleaning the sample with deionized water and absolute ethyl alcohol for three times to obtain a CuSe sample;
1g of CuSe sample and FeCl with a mass ratio of 25wt% were weighed 3 Adding into 30ml of absolute ethanol, stirring for 15min; adding 0.72g of sodium acetate and 10ml of deionized water as a surfactant to the stirred solution, and stirring for 1h to obtain a solution C;
placing the solution C in a reaction vessel made of polytetrafluoroethylene, and heating at 200 ℃ for 24 hours; after cooling, washing the obtained sample with deionized water and absolute ethyl alcohol for three times respectively; all samples after centrifugation were dried at 60℃for 12 hours to obtain a CF-25 complex product.
The CF-25 was placed in a mercury vapor generator for mercury removal assessment tests in a simulated exhaust environment. In this process, the flow rate of the gas stream was adjusted to 1.2L/min, and the carrier gas was adjusted to 0.2L/min. The whole reaction was carried out in a quartz tube having an inner diameter of 6mm using a fixed bed reactor as a reaction platform, the mass of the adsorbent was controlled at 50mg, and the reaction was carried out at 80/160/240℃for 2 hours, respectively, to simulate the temperature of the front end of the ESP.
Example 2
1.0g of sodium hydroxide and 2g of selenium powder are dissolved in 20ml of diluted hydrazine hydrate solution to obtain a mixed solution A; 4.0g of copper sulfate was dissolved in 40ml of deionized water to obtain a mixed solution B;
the mixed solution A, B was mixed and further aged by stirring for 2 hours; taking out the sample, and respectively cleaning the sample with deionized water and absolute ethyl alcohol for three times to obtain a CuSe sample;
1g of CuSe sample and 15wt% FeCl by mass were weighed 3 Adding into 30ml of absolute ethanol, and stirring for 15min; adding 0.72g of sodium acetate and 10ml of deionized water as a surfactant to the stirred solution, and stirring for 1h to obtain a solution C;
placing the solution C in a reaction vessel made of polytetrafluoroethylene, and heating at 200 ℃ for 24 hours; after cooling, washing the obtained sample with deionized water and absolute ethyl alcohol for three times respectively; all samples after centrifugation were dried at 60℃for 12 hours to obtain a CF-15 complex product.
The CF-15 was placed in a mercury vapor generator for mercury removal assessment tests in a simulated exhaust environment. In this process, the flow rate of the gas stream was adjusted to 1.2L/min, and the carrier gas was adjusted to 0.2L/min. The whole reaction was carried out in a quartz tube having an inner diameter of 6mm using a fixed bed reactor as a reaction platform, the mass of the adsorbent was controlled at 50mg, and the reaction was carried out at 80/160/240℃for 2 hours, respectively, to simulate the temperature of the front end of the ESP.
Example 3
1.0g of sodium hydroxide and 2g of selenium powder are dissolved in 20ml of diluted hydrazine hydrate solution to obtain a mixed solution A; 4.0g of copper sulfate was dissolved in 40ml of deionized water to obtain a mixed solution B;
the mixed solution A, B was mixed and further aged by stirring for 2 hours; taking out the sample, and respectively cleaning the sample with deionized water and absolute ethyl alcohol for three times to obtain a CuSe sample;
1g of CuSe sample and FeCl with a mass ratio of 20wt% were weighed 3 Adding into 30ml of absolute ethanol, and stirring for 15min; adding 0.72g of sodium acetate and 10ml of deionized water as a surfactant to the stirred solution, and stirring for 1h to obtain a solution C;
placing the solution C in a reaction vessel made of polytetrafluoroethylene, and heating at 200 ℃ for 24 hours; after cooling, washing the obtained sample with deionized water and absolute ethyl alcohol for three times respectively; all samples after centrifugation were dried at 60℃for 12 hours to obtain a CF-20 complex product.
The CF-20 was placed in a mercury vapor generator for mercury removal assessment tests in a simulated exhaust environment. In this process, the flow rate of the gas stream was adjusted to 1.2L/min, and the carrier gas was adjusted to 0.2L/min. The whole reaction was carried out in a quartz tube having an inner diameter of 6mm using a fixed bed reactor as a reaction platform, the mass of the adsorbent was controlled at 50mg, and the reaction was carried out at 80/160/240℃for 2 hours, respectively, to simulate the temperature of the front end of the ESP.
Example 4
1.0g of sodium hydroxide and 2g of selenium powder are dissolved in 20ml of diluted hydrazine hydrate solution to obtain a mixed solution A; 4.0g of copper sulfate was dissolved in 40ml of deionized water to obtain a mixed solution B;
the mixed solution A, B was mixed and further aged by stirring for 2 hours; taking out the sample, and respectively cleaning the sample with deionized water and absolute ethyl alcohol for three times to obtain a CuSe sample;
1g of CuSe sample and FeCl with a mass ratio of 30wt% are weighed 3 Adding into 30ml of absolute ethanol and stirring15min; adding 0.72g of sodium acetate and 10ml of deionized water as a surfactant to the stirred solution, and stirring for 1h to obtain a solution C;
placing the solution C in a reaction vessel made of polytetrafluoroethylene, and heating at 200 ℃ for 24 hours; after cooling, washing the obtained sample with deionized water and absolute ethyl alcohol for three times respectively; all samples after centrifugation were dried at 60℃for 12 hours to obtain a CF-30 complex product.
The CF-30 was placed in a mercury vapor generator for mercury removal assessment tests in a simulated exhaust environment. In this process, the flow rate of the gas stream was adjusted to 1.2L/min, and the carrier gas was adjusted to 0.2L/min. The whole reaction was carried out in a quartz tube having an inner diameter of 6mm using a fixed bed reactor as a reaction platform, the mass of the adsorbent was controlled at 50mg, and the reaction was carried out at 80/160/240℃for 2 hours, respectively, to simulate the temperature of the front end of the ESP.
Example 5
1.0g of sodium hydroxide and 2g of selenium powder are dissolved in 20ml of diluted hydrazine hydrate solution to obtain a mixed solution A; 4.0g of copper sulfate was dissolved in 40ml of deionized water to obtain a mixed solution B;
the mixed solution A, B was mixed and further aged by stirring for 2 hours; taking out the sample, and respectively cleaning the sample with deionized water and absolute ethyl alcohol for three times to obtain a CuSe sample;
1g of CuSe sample and 35wt% FeCl by mass were weighed 3 Adding into 30ml of absolute ethanol, and stirring for 15min; adding 0.72g of sodium acetate and 10ml of deionized water as a surfactant to the stirred solution, and stirring for 1h to obtain a solution C;
placing the solution C in a reaction vessel made of polytetrafluoroethylene, and heating at 200 ℃ for 24 hours; after cooling, washing the obtained sample with deionized water and absolute ethyl alcohol for three times respectively; all samples after centrifugation were dried at 60℃for 12 hours to obtain a CF-35 complex product.
The CF-35 was placed in a mercury vapor generator for mercury removal assessment tests in a simulated exhaust environment. In this process, the flow rate of the gas stream was adjusted to 1.2L/min, and the carrier gas was adjusted to 0.2L/min. The whole reaction was carried out in a quartz tube having an inner diameter of 6mm using a fixed bed reactor as a reaction platform, the mass of the adsorbent was controlled at 50mg, and the reaction was carried out at 80/160/240℃for 2 hours, respectively, to simulate the temperature of the front end of the ESP.
Comparative example 1
1.0g of sodium hydroxide and 2g of selenium powder are dissolved in 20ml of diluted hydrazine hydrate solution to obtain a mixed solution A; 4.0g of copper sulfate was dissolved in 40ml of deionized water to obtain a mixed solution B;
the mixed solution A, B was mixed and further aged by stirring for 2 hours; taking out the sample, and respectively cleaning the sample with deionized water and absolute ethyl alcohol for three times to obtain a CuSe sample;
1g of CuSe sample and FeCl with a mass ratio of 25wt% were weighed 3 Adding into 30ml of absolute ethyl alcohol, and stirring for 15min to obtain a solution C;
placing the solution C in a reaction vessel made of polytetrafluoroethylene, and heating at 200 ℃ for 24 hours; after cooling, washing the obtained sample with deionized water and absolute ethyl alcohol for three times respectively; all samples after centrifugation were dried at 60 ℃ for 12 hours to obtain CF-25 complex products.
The mercury removal assessment test was performed in a simulated exhaust environment with CF-25 x placed in a mercury vapor generator. In this process, the flow rate of the gas stream was adjusted to 1.2L/min, and the carrier gas was adjusted to 0.2L/min. The whole reaction was carried out in a quartz tube having an inner diameter of 6mm using a fixed bed reactor as a reaction platform, the mass of the adsorbent was controlled at 50mg, and the reaction was carried out at 80/160/240℃for 2 hours, respectively, to simulate the temperature of the front end of the ESP.
FIG. 1 is an SEM image of a CF-25 composite product obtained in example 1 of the present application, which is seen to exhibit microspheres having an average diameter of 30-50nm, and a tight aggregation of copper selenide and iron oxide is observed.
FIG. 2 is an XRD pattern of the CF-25 composite product obtained in example 1 of the present application, in which characteristic diffraction peaks of copper selenide are observed at 2θ=26.1, 26.6, 28.1, 30.4, 50.9, 56.6°, etc., and Fe is observed at 2θ=24.1, 33.2, 35.6, 40.9, 62.4, etc 2 O 3 Is indicative of successful preparation of the composite product.
Fig. 3 to 5 show the mercury removal rates of the CF-series composite products prepared in examples 1 to 5 of the present application in the environment simulating the low temperature section, the medium temperature section and the high temperature section (80/160/240 ℃) of the flue gas of the power plant, respectively, and it can be seen that the mercury removal rates of the CF-series composite products in the low/medium temperature section can almost reach 100% and are all very stable, and at the same time, the stable mercury removal efficiency is shown at high Wen Duanbiao, and the mercury removal rate of the selenide produced by the process in the high temperature section can only reach about 60-70%, which indicates that the mercury removal effect of the present application is far superior to that of the selenide for industrial use.
Fig. 6 shows the mercury removal rate of the CF-25 composite product prepared in comparative example 1 in the environment simulating the low temperature section, the middle temperature section and the high temperature section (80/160/240 ℃) of the flue gas of the power plant, and it can be seen that the mercury removal rate of the CF-25 composite product in the environment of 80/160/240 ℃ is 82.74%/79.71%/75.16% respectively without adding a surfactant, and compared with the mercury removal rate of the composite product with the surfactant, the mercury removal rate of the composite product is reduced to a certain extent, which indicates that the preferred sodium acetate and deionized water surfactant of the application have an obvious promotion effect on simulating the mercury removal of the flue gas of the power plant.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (5)
1. The preparation method of the copper selenide composite material for mercury removal is characterized by comprising the following steps: comprising the steps of (a) a step of,
1.0g sodium hydroxide and 2.0g selenium powder are dissolved in 20ml diluted hydrazine hydrate solution to obtain a mixed solution A;
4.0g of copper sulfate was dissolved in 40ml of deionized water to obtain a mixed solution B;
mixing the solution A and the solution B together, stirring and further aging, and then cleaning with deionized water and absolute ethyl alcohol for three times to obtain a CuSe sample;
sample CuSe and FeCl 3 Adding into absolute ethanol, stirring, whereinCuSe mass proportionality meter, feCl 3 The addition amount of the catalyst is 15-35 wt%;
adding a surfactant, and continuing stirring to obtain a solution C, wherein the surfactant is 0.72g of sodium acetate and is dissolved in 10ml of deionized water;
heating the solution C in a reaction vessel made of polytetrafluoroethylene at 200deg.C for 24h, cooling, cleaning the obtained sample with deionized water and absolute ethanol for three times, and drying to obtain CuSe/Fe 2 O 3 And (3) compounding the product.
2. The copper selenide composite produced by the method for producing a copper selenide composite for mercury removal according to claim 1.
3. Use of a copper selenide composite for mercury removal according to claim 2, characterized in that: comprises the steps of 2 O 3 The composite material is used as an adsorbent to be placed in a mercury vapor generator simulating a waste environment, and a mercury removal evaluation experiment is carried out.
4. Use of a copper selenide composite for mercury removal according to claim 3, characterized in that: the airflow speed of the mercury vapor generator is regulated to be 1.2L/min, and the carrier gas flow speed is regulated to be 0.2L/min.
5. Use of a copper selenide composite for mercury removal according to claim 3 or 4, characterized in that: the amount of the adsorbent added was 50mg.
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| CN103084145A (en) * | 2013-01-30 | 2013-05-08 | 东南大学 | Ferric-chlorine-modified active carbon adsorbent for removing mercury from smoke |
| CN110694582A (en) * | 2019-10-22 | 2020-01-17 | 中南大学 | Mercury enrichment material for mercury detector, preparation method and application |
| CN110732303A (en) * | 2019-12-05 | 2020-01-31 | 中南大学 | transition metal selenide modified molding demercuration material and preparation method thereof |
| 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 |
| CN113231004A (en) * | 2021-05-28 | 2021-08-10 | 中南大学 | Normal temperature and pressure preparation method and application of metal selenide mercury adsorbent |
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