CN113019351A - Preparation method of three-phase composite photocatalyst for flue gas demercuration - Google Patents

Preparation method of three-phase composite photocatalyst for flue gas demercuration Download PDF

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CN113019351A
CN113019351A CN202110265766.2A CN202110265766A CN113019351A CN 113019351 A CN113019351 A CN 113019351A CN 202110265766 A CN202110265766 A CN 202110265766A CN 113019351 A CN113019351 A CN 113019351A
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phase composite
flue gas
composite photocatalyst
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CN113019351B (en
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李子燕
叶潇
许磊
王学谦
夏仡
刚瑞奇
王朗朗
谢诚
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Kunming University of Science and Technology
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    • 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
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract

The invention discloses a preparation method of a three-phase composite photocatalyst for flue gas mercury removal, and relates to the technical field of photocatalytic mercury removal of flue gas. g-C prepared step by step3N4、MoS2、TiO2Weighing the materials according to the mass ratio of 10-100: 1-20: 1, adding the materials into a beaker, adding a proper amount of absolute ethyl alcohol, magnetically stirring until the powder and the absolute ethyl alcohol are fully mixed, heating and stirring for 2-3 hours until the liquid is completely evaporated, transferring the precipitate to an air blast dryerDrying for 4-5 h at 60-80 ℃ in a drying box, transferring the dried solid into a crucible for roasting at the heating rate of 3-6 ℃/min, heating to 300-350 ℃, preserving heat for 1.5-3 h, and naturally cooling to room temperature to obtain TiO2/MoS2/g‑C3N4The three materials form a heterojunction in the compounding process, the compounding rate of electron-hole pairs is reduced, the photocatalytic activity is greatly improved, and the mercury removal rate reaches 95.7% after 30min under the irradiation of visible light.

Description

Preparation method of three-phase composite photocatalyst for flue gas demercuration
Technical Field
The invention relates to the technical field of flue gas mercury removal by photocatalysis, in particular to a preparation method of a three-phase composite photocatalyst for flue gas mercury removal.
Background
Mercury is an element harmful to human bodies but widely present in the environment, and when mercury accumulates in human bodies to a certain extent, the mercury can damage the nervous system of the human bodies and cause irreversible damage. Coal-fired boiler flue gas is a main pollution source in a mercury pollution emission source, and as the mercury content in coal in China is obviously higher than the average mercury content in coal in foreign countries, the mercury in the flue gas exceeds the standard, the mercury needs to be removed before emission so as to reach the emission standard. At present, adsorbents such as activated carbon and calcium-based adsorbents are mostly used for adsorption removal, but the removal efficiency is low.
With the popularization of the photocatalytic technology, the photocatalyst is also slowly applied to the mercury removal of flue gas. The patent CN107362817A discloses the preparation of a photocatalyst, and bulk phase g-C is prepared3N4Immersing in nitric acid solution, and washing to obtain g-C3N4Nanosheets, and further reacting with TiO2Dissolving in deionized water, mixing, calcining at high temperature to obtain TiO2/g-C3N4The heterojunction photocatalyst can effectively perform photocatalytic oxidation on the flue gas elementary substance mercury in the power plant, and the mercury removal efficiency under the irradiation of the LED lamp reaches more than 70%. Although the removal rate of mercury in the flue gas is greatly improved, the mercury removal rate is influenced by comprehensive factors of use environment and the like in practical use,the mercury removal rate is difficult to meet the emission requirement, so that a photocatalyst with higher mercury removal efficiency needs to be found urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a three-phase composite photocatalyst for flue gas demercuration, and solves the problem of the existing TiO2/g-C3N4The problem that the removal rate of the heterojunction photocatalyst on mercury in the flue gas is difficult to meet the emission standard is solved.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a three-phase composite photocatalyst for flue gas demercuration is characterized by comprising the following steps:
1)g-C3N4the preparation of (1): placing urea in a crucible to roast under a semi-closed condition, heating up to 550-600 ℃ at a heating rate of 8-10 ℃/min, preserving heat for 2-3 h, and naturally cooling to room temperature to obtain light yellow g-C3N4Powder;
2)TiO2the preparation of (1): dissolving titanium sulfate and urea in deionized water, placing the solution in a microwave digestion instrument, preserving heat for 2-3 h at 140-160 ℃, cooling to room temperature, transferring a hydrothermal product to a high-speed centrifuge for centrifugal separation, placing the collected precipitate in a drying box, drying for 10-15 h at 60-80 ℃, and grinding to obtain white powdery amorphous TiO2And (3) pulverizing.
3)MoS2The preparation of (1): dissolving ammonium tetrathiomolybdate powder in a mixed solution of absolute ethyl alcohol and deionized water, stirring for 1-2 hours, then dropping a certain amount of hydrazine hydrate into the solution, placing the mixed solution in a microwave digestion instrument, preserving heat for 10-15 minutes at 180-200 ℃, and obtaining a hydrothermal product after cooling the mixed solution to room temperature; transferring the obtained hydrothermal product to a high-speed centrifuge for centrifugal separation, transferring the obtained product to a blast drying oven, drying at 40-50 ℃ for 6-8 h, and grinding to obtain powdery MoS2；
4) G to C3N4、MoS2、TiO2Weighing the materials according to the mass ratio of 10-100: 1-20: 1, adding the materials into a beaker, adding a proper amount of absolute ethyl alcohol, and performing magnetic forceStirring until the powder and absolute ethyl alcohol are fully mixed, heating and stirring for 2-3 hours until liquid is completely evaporated, transferring the precipitate into a blast drying oven to be dried for 4-5 hours at the temperature of 60-80 ℃, transferring the dried solid into a crucible to be roasted, raising the temperature to 300-350 ℃, keeping the temperature for 1.5-3 hours, and naturally cooling to room temperature to obtain the three-phase composite photocatalyst.
The further technical scheme is that the mass ratio of the titanium sulfate to the urea in the step 2) is 2:1, and the volume ratio of the urea to the deionized water is 1 g: stirring for 3-5 h under magnetic stirring after mixing titanium sulfate, urea and deionized water by 25mL, transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, and then putting the reaction kettle into a microwave digestion instrument, wherein the heating rate in the microwave digestion instrument is 10 ℃/min.
The further technical scheme is that the volume ratio of the mass of the ammonium tetrathiomolybdate to the hydrazine hydrate, the absolute ethyl alcohol and the deionized water in the step 3) is 1 g: 20mL of: 100mL of: 100 mL.
The further technical scheme is that the adding amount of the powder in the step 4) is 0.1-1 g/L.
A further technical proposal is that the hydrothermal product is centrifuged for 10min at 8000 rpm.
The reaction mechanism is as follows: graphite phase carbon nitride (g-C)3N4) Is a nonmetal semiconductor photocatalyst with low price, no pollution and high visible light absorption coefficient and single g-C3N4The photocatalytic performance is poor. TiO 22Is a traditional wide band gap photocatalyst, has no pollution to the environment, and is mixed with g-C3N4The photocatalyst prepared is a single g-C photocatalyst3N4The photocatalysis performance is good, but the practical use requirement is difficult to meet. Molybdenum sulfide (MoS)2) Belongs to low-toxicity transition metal sulfides, and has a graphene-like laminated structure, MoS2The band gap width of the composite material is about 1.9eV, the composite material has good photoelectric property under the irradiation of visible light, and the composite material is mainly used for photocatalytic hydrogen production. The three are mixed and calcined to be compounded into TiO2/MoS2/g-C3N4Three-phase composite photocatalytic material, wherein P is formed by the three materials in the compounding processthe-N heterojunction promotes the separation and transmission of electron-hole pairs, increases the absorption utilization rate of light, greatly improves the photocatalytic activity, and achieves a mercury removal rate of 95.7% after 30min under the irradiation of visible light.
Compared with the prior art, the invention has the beneficial effects that: provides a preparation method of a three-phase composite photocatalyst with simple preparation process, and g-C prepared step by step3N4、MoS2、TiO2Adding into anhydrous ethanol at a certain proportion, magnetically stirring until the powder is fully mixed with the anhydrous ethanol, heating and evaporating, drying the precipitate, transferring into a crucible, roasting, and naturally cooling to obtain TiO2/MoS2/g-C3N4The three materials form a heterojunction in the compounding process, the compounding rate of electron-hole pairs is reduced, the photocatalytic activity is greatly improved, and the mercury removal rate reaches 95.7% after 30min under the irradiation of visible light. In the invention, the roasting is carried out in the air atmosphere, the conditions are simple, and the industrial production is convenient.
Drawings
FIG. 1 is a microscopic view of a three-phase composite photocatalytic material obtained in the present invention.
FIG. 2 is a diagram showing the photocatalytic performance of the three-phase composite photocatalytic material obtained in the present invention.
FIG. 3 is a flow chart of a photocatalytic mercury removal process.
FIG. 4 is a graph of mercury removal rate of the three-phase composite photocatalytic material obtained in the present invention after the lamp is turned on.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
This example provides a three-phase composite photocatalyst TiO2/MoS2The preparation method of the/g-C3N 4 comprises the following steps:
(1) 20g of urea was placed in a crucible under an air atmosphereSealing and roasting, heating up at the rate of 8-9 ℃/min to 550 ℃, keeping the temperature for 2-3 h, and naturally cooling to room temperature to obtain light yellow g-C3N4And (3) powder.
(2) Dissolving 8g of titanium sulfate and 4g of urea in 100mL of deionized water, magnetically stirring for about 2.5 hours, transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, preserving heat for 2 hours at 140 ℃ in a microwave digestion instrument, cooling to room temperature, centrifuging at 8000 rpm to obtain white precipitates, adding deionized water and absolute ethyl alcohol, and centrifuging for three times respectively to neutrality. Drying the collected precipitate at 60 deg.C for 10 hr, and grinding to obtain white powdery amorphous TiO2And (3) powder.
(3) 0.5g of (NH)4)2MoS4The powder was dissolved in a mixed solution of 50mL of anhydrous ethanol and 50mL of deionized water and stirred for 1 hour, followed by adding 10mL of N2H4·H2And O is dripped into the solution. Pouring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and preserving the heat for 10 minutes at 200 ℃ in a microwave digestion instrument, wherein the heating rate is 10 ℃/min. After the mixed solution is cooled to room temperature, the obtained nano MoS is obtained2Centrifuging at 8000 rpm for 10min for purification, adding deionized water and anhydrous ethanol, centrifuging to neutrality, drying at 40 deg.C in an air drying oven for 6 hr, and grinding to obtain powdered MoS2。
(4) Taking the obtained TiO2、MoS2And g-C3N4According to the mass ratio of 1: 2: 20g of the three-phase composite photocatalyst is weighed, the 2g of the three-phase composite photocatalyst is placed into a 100ml beaker, 60ml of absolute ethyl alcohol is added, magnetic stirring is carried out for 15 hours until powder and the absolute ethyl alcohol are fully mixed, the mixture is heated and stirred for 2 hours at 70 ℃ until the absolute ethyl alcohol is completely evaporated, the mixture is transferred into a forced air drying oven to be dried for 4 hours at 60 ℃, the dried solid is transferred into a crucible, the heating rate is 3-5 ℃/min, and the mixture is heated to 350 ℃ to be roasted for 2 hours, so that the three-phase.
Example 2
This example provides a three-phase composite photocatalyst TiO2/MoS2/g-C3N4The preparation method comprises the following steps:
(1) 20g of urea is placed in a crucible and semi-closed baked in an air atmosphereHeating at the heating rate of 9-10 ℃/min to 580 ℃, keeping the temperature for 2-3 h, and naturally cooling to room temperature to obtain light yellow g-C3N4And (3) powder.
(2) Dissolving 8g of titanium sulfate and 4g of urea in 100mL of deionized water, magnetically stirring for about 2.5h, transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, preserving heat for 2.5h at 150 ℃ in a microwave digestion instrument, cooling to room temperature, centrifuging at 8000 rpm to obtain white precipitate, adding deionized water and absolute ethyl alcohol, and respectively centrifuging for three times until the white precipitate is neutral. Drying the collected precipitate at 70 deg.C for 12 hr, and grinding to obtain white powdery amorphous TiO2And (3) powder.
(3) 0.5g of (NH)4)2MoS4The powder was dissolved in a mixed solution of 50mL of absolute ethanol and 50mL of deionized water and stirred for 1.5h, followed by 10mL of N2H4·H2And O is dripped into the solution. Pouring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and keeping the temperature of 180 ℃ for 12 minutes in a microwave digestion instrument, wherein the heating rate is 10 ℃/min. After the mixed solution is cooled to room temperature, the obtained nano MoS is obtained2Centrifuging at 8000 rpm for 10min for purification, adding deionized water and anhydrous ethanol, centrifuging to neutrality, drying at 45 deg.C in blast drying oven for 7 hr, and grinding to obtain powdered MoS2。
(4) Taking the obtained TiO2、MoS2And g-C3N4According to the mass ratio of 1: 10: 60 g of the three-phase composite photocatalyst is weighed, the 2g of the three-phase composite photocatalyst is placed into a 100ml beaker, 60ml of absolute ethyl alcohol is added, magnetic stirring is carried out for 15 hours until powder and the absolute ethyl alcohol are fully mixed, the mixture is heated and stirred for 3 hours at 60 ℃ until the absolute ethyl alcohol is completely evaporated, the mixture is transferred into a forced air drying oven to be dried for 4.5 hours at 70 ℃, the dried solid is transferred into a crucible, the heating rate is 4-6 ℃/min, and the mixture is heated to 300 ℃ and roasted for 3 hours to obtain the three-phase composite photocatalyst.
Example 3
This example provides a three-phase composite photocatalyst TiO2/MoS2/g-C3N4The preparation method comprises the following steps:
(1) 20g of urea is placed in a crucible and semi-closed baked in an air atmosphereHeating at the heating rate of 8-10 ℃/min, heating to 600 ℃, keeping the temperature for 2-3 h, and naturally cooling to room temperature to obtain light yellow g-C3N4And (3) powder.
(2) Dissolving 8g of titanium sulfate and 4g of urea in 100mL of deionized water, magnetically stirring for about 2.5 hours, transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, preserving heat for 3 hours at 160 ℃ in a microwave digestion instrument, cooling to room temperature, centrifuging at 8000 rpm to obtain white precipitates, and adding deionized water and absolute ethyl alcohol to centrifuge for three times respectively to neutrality. Placing the collected precipitate in a drying oven, drying at 80 deg.C for 10 hr, and grinding to obtain white powdery amorphous TiO2And (3) powder.
(3) 0.5g of (NH)4)2MoS4The powder was dissolved in a mixed solution of 50mL of anhydrous ethanol and 50mL of deionized water and stirred for 1 hour, followed by adding 10mL of N2H4·H2And O is dripped into the solution. Pouring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and keeping the temperature of the reaction kettle in a microwave digestion instrument at 200 ℃ for 15 minutes at a heating rate of 10 ℃/min. After the mixed solution is cooled to room temperature, the obtained nano MoS is obtained2Centrifuging at 8000 rpm for 10min for purification, adding deionized water and anhydrous ethanol, centrifuging to neutrality, drying at 50 deg.C for 8 hr, and grinding to obtain powdered MoS2。
(4) Taking the obtained TiO2、MoS2And g-C3N4According to the mass ratio of 1: 20: 133 g of the three-phase composite photocatalyst is weighed, 2g of the three-phase composite photocatalyst is placed into a 100ml beaker, 60ml of absolute ethyl alcohol is added, magnetic stirring is carried out for 15 hours until the powder and the absolute ethyl alcohol are fully mixed, the mixture is heated and stirred for 2 hours at 70 ℃ until the absolute ethyl alcohol is completely evaporated, the mixture is transferred into a forced air drying oven to be dried for 5 hours at 60 ℃, the dried solid is transferred into a crucible, the heating rate is 3-6 ℃/min, and the mixture is roasted for 2.5 hours at 350 ℃ to obtain the three-phase composite photocatalyst.
Example 4
This example provides a three-phase composite photocatalyst TiO2/MoS2/g-C3N4The preparation method comprises the following steps:
(1) semi-closed roasting 20g urea in air atmosphere with a heating rate of 8 toHeating to 550 deg.C at 10 deg.C/min, maintaining for 3 hr, and naturally cooling to room temperature to obtain light yellow g-C3N4And (3) powder.
(2) Dissolving a certain amount of titanium sulfate and urea in 50mL of deionized water, magnetically stirring for about 2.5h, transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, preserving heat for 2h at 140 ℃ in a microwave digestion instrument, cooling to room temperature, centrifuging at 8000 rpm to obtain white precipitate, adding deionized water and absolute ethyl alcohol, and respectively centrifuging for three times until the white precipitate is neutral. Drying the collected precipitate at 60 deg.C for 10 hr, and grinding to obtain white powdery amorphous TiO2And (3) powder.
(3) 0.5g of (NH)4)2MoS4The powder was dissolved in a mixed solution of 50mL of anhydrous ethanol and 50mL of deionized water and stirred for 1 hour, followed by adding 10mL of N2H4·H2And O is dripped into the solution. Pouring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and preserving the heat for 10 minutes at 200 ℃ in a microwave digestion instrument, wherein the heating rate is 10 ℃/min. After the mixed solution is cooled to room temperature, the obtained nano MoS is obtained2Purifying by centrifuging at 8000 rpm for 10min, adding deionized water and anhydrous ethanol, centrifuging to neutrality, drying at 40 deg.C for 6 hr, and grinding to obtain powdered MoS 2.
(4) Taking the obtained TiO2、MoS2And g-C3N4According to the mass ratio of 1: 20: 100 g of the three-phase composite photocatalyst is weighed, the mixture is placed into a 100ml beaker, 60ml of absolute ethyl alcohol is added, magnetic stirring is carried out for 15 hours until the powder and the absolute ethyl alcohol are fully mixed, the mixture is heated and stirred for 2 hours at 70 ℃ until the absolute ethyl alcohol is completely evaporated, the mixture is transferred into a forced air drying oven to be dried for 4 hours at 60 ℃, the dried solid is transferred into a crucible, the heating rate is 3-6 ℃/min, and the mixture is roasted for 2 hours at 350 ℃ to obtain the three-phase composite photocatalyst.
An SEM image of the three-phase composite photocatalyst with magnification of 5 ten thousand times is shown in figure 1, and flaky g-C can be obviously seen3N4And TiO2、MoS2And (3) granules. And g-C thereof3N4The Uv-vis spectrogram is shown in figure 2, and the absorbance of the three-phase composite photocatalyst (composite material) in an ultraviolet region and a visible light region is obviously greater than that of g-C3N4。
The research on the performance of the photocatalytic demercuration is shown in figure 3, and the simulated flue gas flow is 700ml/min and is composed of 10 percent of O by volume2And 90% mercury vapor with nitrogen as the carrier gas. At the beginning of the experiment, the A channel was opened first and the concentration of Hg0 was adjusted to 900 μ g m-3Then, the B channel was opened to allow Hg0 vapor to pass through the catalyst-carrying channel, a small amount of adsorption was started, and after the adsorption equilibrium, the Hg0 concentration was restored to 900. mu.g.m-3And after keeping the adsorption balance for 60min, turning on a light source of a photocatalytic reaction system, wherein the dosage of the three-phase composite photocatalyst is 0.1 g.
As shown in fig. 4, the removal rate of Hg0 rapidly increased after the visible light source was turned on, and reached a steady level after 30 min. The photocatalytic efficiency can reach 95.7%, and when the visible light source is turned off, the Hg0 vapor concentration value is rapidly increased and is restored to the initial concentration.
Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications are possible in the component parts or arrangements of the subject combination arrangement within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts or arrangements, other uses will also be apparent to those skilled in the art.

Claims (5)

1. A preparation method of a three-phase composite photocatalyst for flue gas demercuration is characterized by comprising the following steps:
1)g-C3N4the preparation of (1): placing urea in a crucible to roast under the semi-closed condition, wherein the heating rate is 8 to
Heating to 550-600 ℃ at a speed of 10 ℃/min, preserving heat for 2-3 h, and naturally cooling to room temperature to obtain faint yellow g-C3N4Powder;
2)TiO2the preparation of (1): dissolving titanium sulfate and urea in the solutionPutting the solution in a microwave digestion instrument in deionized water, preserving heat for 2-3 h at 140-160 ℃, cooling to room temperature, transferring a hydrothermal product to a high-speed centrifuge for centrifugal separation, putting the collected precipitate in a drying box, drying for 10-15 h at 60-80 ℃, and grinding to obtain white powdery amorphous TiO2And (3) pulverizing.
3)MoS2The preparation of (1): dissolving ammonium tetrathiomolybdate powder in a mixed solution of absolute ethyl alcohol and deionized water, stirring for 1-2 hours, then dropping a certain amount of hydrazine hydrate into the solution, placing the mixed solution in a microwave digestion instrument, preserving heat for 10-15 minutes at 180-200 ℃, and obtaining a hydrothermal product after cooling the mixed solution to room hydration temperature; transferring the obtained hydrothermal product to a high-speed centrifuge for centrifugal separation, transferring the obtained product to a blast drying oven, drying at 40-50 ℃ for 6-8 h, and grinding to obtain powdery MoS2；
4) G to C3N4、MoS2、TiO2Weighing the materials according to a mass ratio of 10-100: 1-20: 1, adding the materials into a beaker, adding a proper amount of absolute ethyl alcohol, magnetically stirring until the powder and the absolute ethyl alcohol are fully mixed, heating and stirring for 2-3 hours until the liquid is completely evaporated, transferring the precipitate into a forced air drying oven, drying for 4-5 hours at 60-80 ℃, transferring the dried solid into a crucible for roasting, heating to 300-350 ℃ at a heating rate of 3-6 ℃/min, keeping the temperature for 1.5-3 hours, and naturally cooling to room temperature to obtain the three-phase composite photocatalyst.
2. The preparation method of the three-phase composite photocatalyst for mercury removal from flue gas as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 2), the mass ratio of the titanium sulfate to the urea is 2:1, and the volume ratio of the urea to the deionized water is 1 g: and 25mL, mixing titanium sulfate, urea and deionized water, stirring for 3-5 h under magnetic stirring, transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, and then putting the reaction kettle into a microwave digestion instrument.
3. The preparation method of the three-phase composite photocatalyst for mercury removal from flue gas as claimed in claim 1, wherein the preparation method comprises the following steps: the volume ratio of the mass of the ammonium tetrathiomolybdate to the hydrazine hydrate, the absolute ethyl alcohol and the deionized water in the step 3) is 1 g: 20mL of: 100mL of: 100 mL.
4. The preparation method of the three-phase composite photocatalyst for mercury removal from flue gas as claimed in claim 1, wherein the preparation method comprises the following steps: the adding amount of the powder in the step 4) is 0.1-1 g/L.
5. The preparation method of the three-phase composite photocatalyst for mercury removal from flue gas as claimed in claim 1, wherein the preparation method comprises the following steps: the hydrothermal product was centrifuged at 8000 rpm for 10 min.
CN202110265766.2A 2021-03-11 2021-03-11 Application of three-phase composite photocatalyst in flue gas demercuration Active CN113019351B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115108587A (en) * 2022-06-24 2022-09-27 上海交通大学医学院附属仁济医院 Molybdenum disulfide-doped two-dimensional carbon nitrogen compound matrix and preparation method and application thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103974756A (en) * 2011-12-15 2014-08-06 科莱恩公司 Composition and process for mercury removal
CN106881136A (en) * 2017-02-23 2017-06-23 江苏大学 Metal phase molybdenum bisuphide/two dimension carbonitride catalysis material preparation method
CN107362817A (en) * 2017-06-26 2017-11-21 上海电力学院 A kind of preparation method of the adjustable titania modified graphite phase carbon nitride photochemical catalyst of dimension
CN107812541A (en) * 2017-09-30 2018-03-20 昆明理工大学 It is a kind of using metal organic frame body as demercuration catalyst of carrier and preparation method thereof
WO2018082175A1 (en) * 2016-11-07 2018-05-11 杭州同净环境科技有限公司 Composite photo-catalyst, preparation method therefor and application thereof
CN110639589A (en) * 2019-10-11 2020-01-03 常州纳欧新材料科技有限公司 Carbon nitride material with one-dimensional nano structure and preparation method and application thereof
CN111203261A (en) * 2020-03-05 2020-05-29 上海纳米技术及应用国家工程研究中心有限公司 Specific three-layer stacked ternary composite catalyst and preparation method and application thereof
CN111760579A (en) * 2020-07-12 2020-10-13 昆明理工大学 Preparation method and application of tungsten-molybdenum bisulfide composite photocatalyst
CN112058082A (en) * 2020-09-13 2020-12-11 昆明理工大学 Method for removing zero-valent mercury and arsenic hydride by magnetic field in cooperation with photocatalytic oxidation
CN112264075A (en) * 2020-11-09 2021-01-26 华侨大学 High-efficiency demercuration photocatalyst suitable for medium-low temperature condition and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103974756A (en) * 2011-12-15 2014-08-06 科莱恩公司 Composition and process for mercury removal
WO2018082175A1 (en) * 2016-11-07 2018-05-11 杭州同净环境科技有限公司 Composite photo-catalyst, preparation method therefor and application thereof
CN106881136A (en) * 2017-02-23 2017-06-23 江苏大学 Metal phase molybdenum bisuphide/two dimension carbonitride catalysis material preparation method
CN107362817A (en) * 2017-06-26 2017-11-21 上海电力学院 A kind of preparation method of the adjustable titania modified graphite phase carbon nitride photochemical catalyst of dimension
CN107812541A (en) * 2017-09-30 2018-03-20 昆明理工大学 It is a kind of using metal organic frame body as demercuration catalyst of carrier and preparation method thereof
CN110639589A (en) * 2019-10-11 2020-01-03 常州纳欧新材料科技有限公司 Carbon nitride material with one-dimensional nano structure and preparation method and application thereof
CN111203261A (en) * 2020-03-05 2020-05-29 上海纳米技术及应用国家工程研究中心有限公司 Specific three-layer stacked ternary composite catalyst and preparation method and application thereof
CN111760579A (en) * 2020-07-12 2020-10-13 昆明理工大学 Preparation method and application of tungsten-molybdenum bisulfide composite photocatalyst
CN112058082A (en) * 2020-09-13 2020-12-11 昆明理工大学 Method for removing zero-valent mercury and arsenic hydride by magnetic field in cooperation with photocatalytic oxidation
CN112264075A (en) * 2020-11-09 2021-01-26 华侨大学 High-efficiency demercuration photocatalyst suitable for medium-low temperature condition and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JALEEL, UCJR ET AL: "Statistical and experimental studies of MoS2/g-C3N4/TiO2: a ternary Z-scheme hybrid composite", 《JOURNAL OF MATERIALS SCIENCE》, vol. 56, no. 11, 3 January 2021 (2021-01-03), pages 6922 - 6944, XP037353162, DOI: 10.1007/s10853-020-05695-z *
WAN-KUEN JO ET AL: "Synthesis of MoS2 nanosheet supported Z-scheme TiO2/g-C3N4 photocatalysts for the enhanced photocatalytic degradation of organic water pollutants", 《RSC ADV.》, vol. 6, 20 January 2016 (2016-01-20), pages 10487 - 10497 *
丁希楼 等: "Ti02晶体的微波水热法制备及光催化性能研究", 《环境工程学报》, vol. 4, no. 4, 30 April 2010 (2010-04-30), pages 802 *
向斌，崔旭东著: "《二维过渡金属化合物》", 31 December 2017, 中国原子能出版社, pages: 69 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115108587A (en) * 2022-06-24 2022-09-27 上海交通大学医学院附属仁济医院 Molybdenum disulfide-doped two-dimensional carbon nitrogen compound matrix and preparation method and application thereof

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