CN113713757A - Preparation method and product of high-efficiency mercury adsorbent for waste gas liquid - Google Patents

Preparation method and product of high-efficiency mercury adsorbent for waste gas liquid Download PDF

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CN113713757A
CN113713757A CN202111001778.0A CN202111001778A CN113713757A CN 113713757 A CN113713757 A CN 113713757A CN 202111001778 A CN202111001778 A CN 202111001778A CN 113713757 A CN113713757 A CN 113713757A
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adsorbent
mercury
selenium
mixed solution
exhaust gas
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赵永椿
肖日宏
张军营
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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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
    • 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
    • B01J20/06—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
    • B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Abstract

The invention belongs to the technical field related to mercury adsorbents, and discloses a preparation method and a product of a high-efficiency mercury adsorbent for waste gas liquid. The preparation method comprises the following steps: s1 selecting selenide powder, reductant powder and a solvent to mix them to form a mixed solution in which the selenide is reduced to form selenium; s2, adding an adsorbent carrier into the mixed solution, and stirring to enable the selenium to be adsorbed on the adsorbent carrier; s3 adding a PH adjusting agent to the mixed solution processed in step S2 to make the mixed solution alkaline, filtering the mixed solution, and drying the solid obtained by filtering to obtain the desired adsorbent. The invention solves the problems of low mercury adsorbent adsorption efficiency, complex preparation method and high cost.

Description

Preparation method and product of high-efficiency mercury adsorbent for waste gas liquid
Technical Field
The invention belongs to the technical field related to mercury adsorbents, and particularly relates to a preparation method and a product of a high-efficiency mercury adsorbent for waste gas liquid.
Background
Mercury, as a toxic substance with enrichment, gas transmission characteristics and neurotoxicity, can cause headache, fever, general symptoms, skin erythema and other manifestations when accumulated in human body, and causes pollution to atmosphere, soil and water, thus causing great threat to human health and ecological environment. The united nations environmental planning agency states that in 2019, newly published reports on evaluation of global mercury emissions, the emission of mercury by human activities in the world in 2015 reaches 2.15 × 106kg, 12% more than 2010, wherein the coal-fired power plant is the main source of mercury pollution, and the emission limit of flue gas mercury from 1 month and 1 day of 2015 should not exceed 0.03mg/m3. At present, the common methods for recovering mercury in mercury-containing waste are as follows: the method comprises the steps of roasting the mercury in a roasting furnace at high temperature, cooling gaseous mercury into liquid through a condenser and recycling the liquid, wherein the equipment adopted by the method is huge, is not easy to seal, has serious secondary pollution and is not high in recovery rate; in the chemical oxidation method, nitric acid, hydrogen peroxide, sodium hypochlorite and the like have strong oxidizing property, and the impurity metal is oxidized and enters the solution, so that the aim of separating the impurities from the mercury is fulfilled. By utilizing the method, part of the oxidant has complex reaction and the mercury removal efficiency is not high. The adsorption method utilizes an adsorbent to recover mercury, for example, activated carbon is selected to adsorb mercury, but the cost is very high, post treatment is needed, and the efficiency is not high.
In patent CN101497029, sulfur is loaded on activated carbon to prepare a sulfur-loaded adsorbent for demercuration, although the method adopts low-cost sulfur for modification loading, the method does not mention the demercuration efficiency and other related indexes of the adsorbent in practical application, and the adsorption effect of the sulfur-loaded adsorbent cannot be proved; patent CN107051045A provides a sponge loaded with nano selenium and chemical preparation and application thereof, and a preparation method of mercury-removing wallpaper, wherein sodium selenite is reduced by ascorbic acid and loaded on the surface of the sponge, but waste gas is easily generated in the manufacturing process of the method; patent CN101497029 uses low-cost sulfur and activated carbon to prepare the demercuration adsorbent, but only the preparation method of the adsorbent is introduced, and the demercuration effect of the sulfur-loaded adsorbent is not described, and the activated carbon injection has a disadvantage of high cost.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a preparation method and a product of a high-efficiency mercury adsorbent for exhaust gas liquid, and solves the problems of low adsorption efficiency, complex preparation method and high cost of the mercury adsorbent.
To achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a high efficiency mercury adsorbent for exhaust gas liquids, the method comprising the steps of:
s1 selecting selenide powder, reductant powder and a solvent to mix them to form a mixed solution in which the selenide is reduced to form selenium;
s2, adding an adsorbent carrier into the mixed solution, and stirring to enable the selenium to be adsorbed on the adsorbent carrier;
s3 adding a PH adjusting agent to the mixed solution processed in step S2 to make the mixed solution alkaline, filtering the mixed solution, and drying the solid obtained by filtering to obtain the desired adsorbent.
Further preferably, in step S1, the selenide is selenate, selenite, or selenium dioxide.
Further preferably, in step S1, the reducing agent is vitamin C, sodium borohydride, glutathione, hydrazine hydrate or lithium aluminum hydride.
Further preferably, in step S1, the adsorbent support is spherical silica or gamma alumina microspheres.
Further preferably, the particle size of the adsorbent is less than 100 microns.
Further preferably, in step S3, the selenium-loaded mercury adsorbents each have an adsorption efficiency of 90% or more.
Further preferably, in step S3, the PH adjusting agent is a sodium hydroxide solution.
Further preferably, in step S3, the drying temperature is 100 ℃ to 150 ℃ and the drying time is 8h to 12 h.
Further preferably, in step S1, the solvent is deionized water.
According to another aspect of the present invention, there is provided a mercury sorbent obtained by the above-described preparation method.
Generally, compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. according to the invention, the adsorbent carrier is adopted to adsorb selenium, and the mercury adsorbent is prepared by utilizing the affinity of selenium and mercury, wherein the prepared selenium-loaded adsorbent not only has a strong adsorption effect on gaseous mercury, but also can synergistically remove mercury ions in gypsum slurry of a coal-fired power plant by using the adsorbent after demercuration, so that mercury in gas phase and liquid phase is enriched to the surface of the adsorbent;
2. the spherical silicon dioxide/gamma-type alumina serving as the adsorbent carrier selected by the invention has small particle size (100 microns), large specific surface area, large selenium-carrying capacity and long service life, and a small amount of adsorbent can absorb a large amount of mercury-containing gas;
3. after the mercury is adsorbed by the selenium-loaded mercury adsorbent prepared by the method, the adsorbent after mercury removal is treated by a mercury adsorbent dissolving method, and the carrier of the inactivated selenium-loaded adsorbent is dissolved, so that the product mercury selenide is obtained, and the mercury selenide can be recycled;
4. in the invention, after step S2, a PH adjusting agent is added to the mixed solution to make the solution alkaline, which aims to make the solution neutral, and since the peracid and the alkali will react with the carrier silica of the adsorbent to cause the loss of the adsorbent during the preparation, the alkali is added to neutralize the acidic solution formed by the selenate ions;
5. the adsorbent matrix silicon dioxide/gamma-type alumina in the invention is purchased on the market, the material is easy to obtain, the preparation cost is reduced, the preparation method is simple, the operation condition is mild, the mass preparation can be carried out, and the adsorbent matrix silicon dioxide/gamma-type alumina is used for removing mercury in waste gas in a fixed bed filling mode and is put into industrial production.
Drawings
FIG. 1 is a schematic diagram of a mercury sorption system constructed in accordance with a preferred embodiment of the invention;
FIG. 2 is an electron micrograph of silica constructed in accordance with a preferred embodiment of the invention;
FIG. 3 is an electron micrograph of a selenium loaded sorbent constructed in accordance with a preferred embodiment of the invention;
FIG. 4 is an XPS spectrum of a selenium loaded sorbent;
FIG. 5 is an XRD pattern of the selenium loaded sorbent;
FIG. 6 is an XPS spectrum of Hg for a demercuration adsorbent;
fig. 7 is an XPS spectrum of Se of a demercuration adsorbent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is 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. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention utilizes a reducing agent (vitamin C/sodium borohydride/glutathione/hydrazine hydrate/lithium aluminum hydride and the like) to reduce the valence state selenium in selenic acid crystals/selenite/selenium dioxide and other selenides, an adsorbent carrier (spherical silicon dioxide, gamma-shaped alumina microspheres) is placed in a solution for impregnation, stirring and loading, 0.1mol/L sodium hydroxide solution is utilized to adjust the pH value of the solution to be alkaline, the reacted solution is filtered to obtain a solid, the solid is dried at normal temperature for 12 hours and then dried at 100-150 ℃ for 8-12 hours, and then the silicon dioxide loaded with selenium, namely the selenium-loaded adsorbent is obtained.
The use method of the high-efficiency mercury adsorbent for the waste gas and the liquid comprises the following steps:
FIG. 1 is a schematic view of a mercury adsorption system, in which a mercury tube is placed at one end of a U-shaped tube, silica gel is placed at the other end,for absorbing water, N, from gases2Starting experimental instruments such as a water bath, a temperature controller and a heating belt as mercury-carrying gas, controlling the temperature of the water bath at 70 deg.C, and maintaining the mercury concentration in the pipeline at 100 μ g/m3And the selenium-loaded adsorbent is arranged in a reactor bed layer in the tubular furnace to adsorb and fix the gaseous mercury. And the gas flows through the tubular furnace reactor and then is introduced into an air inlet pipeline of the on-line monitoring mercury detector to monitor the change of the concentration of the gas mercury in real time, and an air outlet pipeline of the gas is introduced into the activated carbon absorber to absorb the residual toxic gas mercury. The selenium-loaded adsorbent can effectively absorb gaseous elemental mercury, and then the selenium-loaded adsorbent is placed in gypsum slurry, wherein the gypsum slurry (gypsum and desulfurization wastewater) is rich in a large amount of divalent mercury ions, and the mercury ions in the gypsum slurry can be captured to an undetectable level by the selenium-loaded adsorbent.
The mercury concentration of the gypsum penetrating fluid is 10.4 mug/L, the retention time of the mercury-containing adsorbent in the solution is 15-20min, and the mercury concentration of the gypsum penetrating fluid is obviously reduced after the mercury-containing adsorbent is mixed with the mercury-rich selenium-carrying adsorbent. After the adsorbent is saturated to mercury adsorption capacity in waste gas and liquid, as the microsphere silicon dioxide and the gamma-type alumina microspheres are dissolved in a strong alkali solution, the carrier carrying the selenium adsorbent after mercury removal is eluted by using a high-concentration sodium hydroxide solution, in addition, mercury selenide is stable in property and insoluble in strong alkali, and then the mercury selenide is filtered and extracted, and the mercury selenide is used as an important electronic device material, so that the resource utilization of mercury is realized.
The present invention will be further described with reference to specific examples.
Example 1
Dissolving 0.4g selenic acid crystal with 100ml deionized water, adding 2.8g vitamin C, magnetic stirring for 0.5 hr, adding 1g gamma-type alumina into the above solution, soaking and stirring with magnetic stirrer for 0.5 hr, and adding seleniumLoading a simple substance on the surface of gamma-type aluminum oxide to obtain a suspension; and filtering the suspension to obtain a precipitate, washing the precipitate for several times by using a certain amount of ethanol and deionized water, drying at room temperature for 12 hours, and transferring to 100 ℃ for drying for 12 hours to obtain the selenium-loaded adsorbent. Weighing 300mg selenium-loaded adsorbent, placing in a tube furnace reactor, and regulating gas mercury carrier gas (N)2) At a rate of 0.15L/min, diluting gas (N)2) The speed is 1.05L/min, and the total flow of the simulated smoke is 1.2L/min. The reaction time is 2h, and the result shows that the efficiency of removing mercury in the example 1 can reach 98.9%, and the mercury adsorption capacity is 190.1 mg/g. Then 50mg of the adsorbent after demercuration is placed in a solution with the mercury content of 250 mug/L, after shaking for 15min, the mercury concentration in the penetrating fluid is detected by an ICP-MS method and is reduced to 20.6 mug/L, and the value is far lower than the hazardous waste supervision limit (200 mug/L) of the United states environmental protection agency.
Example 2
Fully dissolving 0.5g of selenic acid crystals by using 100ml of deionized water, adding 0.6g of sodium borohydride, carrying out magnetic stirring for 0.5h, weighing 1g of gamma-type alumina, putting the gamma-type alumina into the solution, carrying out dipping stirring for 0.5h by using a magnetic stirrer, and loading a selenium simple substance on the surface of the gamma-type alumina to obtain a suspension; and filtering the suspension to obtain a precipitate, washing the precipitate for several times by using a certain amount of ethanol and deionized water, drying at room temperature for 12 hours, and transferring to 150 ℃ for drying for 8 hours to obtain the selenium-loaded adsorbent. Weighing 300mg selenium-loaded adsorbent, placing in a tube furnace reactor, and regulating gas mercury carrier gas (N)2) At a rate of 0.15L/min, diluting gas (N)2) The speed is 1.05L/min, and the total flow of the simulated smoke is 1.2L/min. The reaction time is 2h, and the result shows that the mercury removal efficiency of the embodiment 2 can reach 93.9%, and the mercury adsorption capacity is 253.3 mg/g. Then 50mg of the adsorbent after demercuration is placed in a solution with the mercury content of 250 mug/L, after shaking for 15min, the mercury concentration in the penetrating fluid is detected by an ICP-MS method and is reduced to 13.1 mug/L, and the value is far lower than the hazardous waste supervision limit (200 mug/L) of the United states environmental protection agency.
Example 3
Mixing 0.3g powdered sodium/potassium/calcium selenate and 1.1g sodium borohydride, and deionizing with 100mlFully dissolving water at room temperature, obtaining a solution containing elemental selenium after the solution is light red, weighing 1g of silicon dioxide powder, placing the silicon dioxide powder into the solution, soaking and stirring the solution for 0.5h by using a magnetic stirrer, loading the elemental selenium on the surface of silicon dioxide to obtain a suspension, filtering the suspension to obtain a precipitate, washing the precipitate for several times by using a certain amount of ethanol and deionized water, drying the precipitate at room temperature for 12h, and transferring the precipitate to 120 ℃ for drying for 10h to obtain the selenium-loaded adsorbent. Weighing 300mg selenium-loaded adsorbent, placing in a tubular reaction furnace, fixing the adsorbent in the reaction tube bed layer, and regulating gas mercury carrier gas (N)2) At a rate of 0.15L/min, diluting gas (N)2) The speed is 1.05L/min, and the total flow of the simulated smoke is 1.2L/min. Initial mercury concentration of 100. mu.g/m3The reaction time is 2h, the reaction temperature is 100 ℃, the reaction time is about 5 minutes, and the concentration is rapidly reduced to 2 mu g/m3About, demercuration efficiency is maintained above 90% for a long time, meanwhile, a life monitoring experiment of the adsorbent is carried out, the selenium-loaded adsorbent can maintain a demercuration experiment for 168 hours, and the adsorption capacity reaches 256.3 mg/g. And then placing the sample after demercuration in a simulated gypsum penetrating fluid with the mercury content of 250 mug/L, mixing and shaking for 15min, detecting the mercury concentration in the penetrating fluid by using an ICP-MS method, and reducing the mercury concentration to 35.7 mug/L, wherein the value is far lower than the hazardous waste supervision limit (200 mug/L) of the United states environmental protection agency.
Example 4
Selecting 0.15g of powdery sodium/potassium/calcium selenate and 3.8g of glutathione to mix, fully dissolving the mixture with 100ml of deionized water at room temperature, obtaining a solution containing elemental selenium after the solution is light red, weighing 1g of silicon dioxide powder, placing the silicon dioxide powder into the solution, soaking and stirring the solution with a magnetic stirrer for 0.5h, loading the elemental selenium on the surface of silicon dioxide to obtain a suspension, filtering the suspension to obtain a precipitate, washing the precipitate for several times with a certain amount of ethanol and deionized water, drying the precipitate at room temperature for 12h, and transferring the precipitate to 130 ℃ for drying for 12h to obtain the selenium-loaded adsorbent. Weighing 300mg selenium-loaded adsorbent, placing in a tubular reaction furnace, fixing the adsorbent in the reaction tube bed layer, and regulating gas mercury carrier gas (N)2) At a rate of 0.15L/min, diluting gas (N)2) The speed is 1.05L/min, and the total flow of the simulated smoke is1.2L/min. Initial mercury concentration of 100. mu.g/m3The reaction time is 2h, the reaction temperature is 100 ℃, the reaction time is about 5 minutes, and the concentration is rapidly reduced to 2 mu g/m3About, demercuration efficiency is maintained above 90% for a long time, meanwhile, a life monitoring experiment of the adsorbent is carried out, the selenium-loaded adsorbent can maintain a demercuration experiment for 168 hours, and the adsorption capacity reaches 400 mg/g. And then placing the sample after demercuration in a simulated gypsum penetrating fluid with the mercury content of 250 mug/L, mixing and shaking for 15min, detecting the mercury concentration in the penetrating fluid by using an ICP-MS method, and reducing the mercury concentration to 10.2 mug/L, wherein the value is far lower than the hazardous waste supervision limit (200 mug/L) of the United states environmental protection agency.
Example 5
Selecting 1.5g of powdery sodium/potassium/calcium selenate and 1.7 g of hydrazine hydrate, mixing, fully dissolving with 100ml of deionized water at room temperature, obtaining a solution containing elemental selenium after the solution is light red, weighing 1g of silicon dioxide powder, placing the silicon dioxide powder into the solution, soaking and stirring for 0.5h by using a magnetic stirrer, loading the elemental selenium on the surface of silicon dioxide to obtain a suspension, filtering the suspension to obtain a precipitate, washing the precipitate for several times by using a certain amount of ethanol and deionized water, drying at room temperature for 12h, and transferring to 100 ℃ for drying for 12h to obtain the selenium-loaded adsorbent. Weighing 300mg selenium-loaded adsorbent, placing in a tubular reaction furnace, fixing the adsorbent in the reaction tube bed layer, and regulating gas mercury carrier gas (N)2) At a rate of 0.15L/min, diluting gas (N)2) The speed is 1.05L/min, and the total flow of the simulated smoke is 1.2L/min. Initial mercury concentration of 100. mu.g/m3The reaction time is 2h, the reaction temperature is 100 ℃, the reaction time is about 5 minutes, and the concentration is rapidly reduced to 2 mu g/m3About, demercuration efficiency is maintained above 90% for a long time, meanwhile, a life monitoring experiment of the adsorbent is carried out, the selenium-loaded adsorbent can maintain a demercuration experiment for 168 hours, and the adsorption capacity reaches 383.6 mg/g. And then placing the sample after demercuration in a simulated gypsum penetrating fluid with the mercury content of 250 mug/L, mixing and shaking for 15min, detecting the mercury concentration in the penetrating fluid by using an ICP-MS method, and reducing the mercury concentration to 25.2 mug/L, wherein the value is far lower than the hazardous waste supervision limit (200 mug/L) of the United states environmental protection agency.
Example 6
Selecting 0.15g of powdery sodium/potassium/calcium selenate and 3.8g of lithium aluminum hydroxide for mixing, fully dissolving the mixture by 100ml of deionized water at room temperature, obtaining a solution containing elemental selenium after the solution is light red, weighing 1g of silicon dioxide powder, placing the silicon dioxide powder into the solution, soaking and stirring the solution by a magnetic stirrer for 0.5h, loading the elemental selenium on the surface of silicon dioxide to obtain a suspension, filtering the suspension to obtain a precipitate, washing the precipitate for several times by using a certain amount of ethanol and deionized water, drying the precipitate at room temperature for 12h, and transferring the precipitate to 100 ℃ for drying for 12h to obtain the selenium-loaded adsorbent. Weighing 300mg selenium-loaded adsorbent, placing in a tubular reaction furnace, fixing the adsorbent in the reaction tube bed layer, and regulating gas mercury carrier gas (N)2) At a rate of 0.15L/min, diluting gas (N)2) The speed is 1.05L/min, and the total flow of the simulated smoke is 1.2L/min. Initial mercury concentration of 100. mu.g/m3The reaction time is 2h, the reaction temperature is 100 ℃, the reaction time is about 5 minutes, and the concentration is rapidly reduced to 2 mu g/m3About, demercuration efficiency is maintained above 90% for a long time, meanwhile, a life monitoring experiment of the adsorbent is carried out, the selenium-loaded adsorbent can maintain a demercuration experiment for 168 hours, and the adsorption capacity reaches 294.5 mg/g. And then placing the sample after demercuration in a simulated gypsum penetrating fluid with the mercury content of 250 mug/L, mixing and shaking for 15min, detecting the mercury concentration in the penetrating fluid by using an ICP-MS method, and reducing the mercury concentration to 80.4 mug/L, wherein the value is far lower than the hazardous waste supervision limit (200 mug/L) of the United states environmental protection agency.
Example 7
Selecting 0.2g of powdery selenium dioxide and 1.4g of glutathione to mix, fully dissolving the selenium dioxide and the glutathione in 100ml of deionized water at room temperature, obtaining a solution containing elemental selenium after the solution is light red, weighing 1g of silicon dioxide powder, placing the silicon dioxide powder in the solution, soaking and stirring the silicon dioxide powder for 0.5h by using a magnetic stirrer, loading the elemental selenium on the surface of silicon dioxide to obtain a suspension, filtering the suspension to obtain a precipitate, washing the precipitate for several times by using a certain amount of ethanol and deionized water, drying the precipitate at room temperature for 12h, and transferring the precipitate to 100 ℃ for drying for 12h to obtain the selenium-loaded adsorbent. Weighing 300mg selenium-loaded adsorbent, placing in a tubular reaction furnace, fixing the adsorbent in the reaction tube bed layer, and regulating gas mercury carrier gas (N)2) At a rate of 0.15L/min, diluting gas (N)2) The speed is 1.05L/min, and the total flow of the simulated smoke is 1.2L/min. Initial mercury concentration of 100. mu.g/m3The reaction time is 2h, the reaction temperature is 100 ℃, the reaction time is about 5 minutes, and the concentration is rapidly reduced to 2 mu g/m3About, demercuration efficiency is maintained above 90% for a long time, meanwhile, a life monitoring experiment of the adsorbent is carried out, the selenium-loaded adsorbent can maintain a demercuration experiment for 168 hours, and the adsorption capacity reaches 301.2 mg/g. And then placing the sample after demercuration in a simulated gypsum penetrating fluid with the mercury content of 250 mug/L, mixing and shaking for 15min, detecting the mercury concentration in the penetrating fluid by using an ICP-MS method, and reducing the mercury concentration to 10.8 mug/L, wherein the value is far lower than the hazardous waste supervision limit (200 mug/L) of the United states environmental protection agency.
Example 8
1g of silicon dioxide is immersed in a solution of sodium selenite mixed with hydrazine hydrate, wherein the molar ratio of the sodium selenite to the hydrazine hydrate is 1: 3, fully stirring for 0.5h at room temperature, and loading the selenium simple substance on the surface of the silicon dioxide to obtain suspension; and filtering the suspension to obtain a precipitate, washing the precipitate for several times by using a certain amount of ethanol and deionized water, drying at room temperature for 12 hours, and transferring to 100 ℃ for drying for 12 hours to obtain the selenium-loaded adsorbent. Weighing 300mg selenium-loaded adsorbent, placing in a tube furnace reactor, and regulating gas mercury carrier gas (N)2) At a rate of 0.15L/min, diluting gas (N)2) The speed is 1.05L/min, and the total flow of the simulated smoke is 1.2L/min. The reaction time is 2h, and the result shows that the efficiency of removing mercury in the example 8 can reach 95.7%, and the mercury adsorption capacity is 190.6 mg/g. Then 50mg of the adsorbent after demercuration is placed in a solution with the mercury content of 250 mug/L, after shaking for 15min, the mercury concentration in the penetrating fluid is detected by an ICP-MS method and is reduced to 18.4 mug/L, and the value is far lower than the hazardous waste supervision limit (200 mug/L) of the United states environmental protection agency.
Example 9
1g of silicon dioxide is immersed in a mixed solution of potassium selenite/sodium selenite and sodium borohydride, wherein the molar ratio of the potassium selenite/sodium selenite to the sodium borohydride is 2: 3, fully stirring for 0.5h at room temperature, and loading the selenium simple substance on the surface of the silicon dioxide to obtain suspension; rear endAnd filtering the suspension to obtain a precipitate, washing the precipitate for several times by using a certain amount of ethanol and deionized water, drying at room temperature for 12 hours, and transferring to 100 ℃ for drying for 12 hours to obtain the selenium-loaded adsorbent. Weighing 300mg selenium-loaded adsorbent, placing in a tube furnace reactor, and regulating gas mercury carrier gas (N)2) At a rate of 0.15L/min, diluting gas (N)2) The speed is 1.05L/min, and the total flow of the simulated smoke is 1.2L/min. The reaction time is 2h, and the result shows that the efficiency of removing mercury in the example 9 can reach 94.3%, and the mercury adsorption capacity is 290.6 mg/g. Then 50mg of the adsorbent after demercuration is placed in a solution with the mercury content of 250 mug/L, after shaking for 15min, the mercury concentration in the penetrating fluid is detected by an ICP-MS method and is reduced to 40.4 mug/L, and the value is far lower than the hazardous waste supervision limit (200 mug/L) of the United states environmental protection agency.
FIGS. 2 and 3 show SiO2And Se/SiO2Form of (2), SiO2Is irregular granular and has relatively smooth surface. For Se/SiO2The rod-shaped structure appears on the surface layer, which indicates that nano-selenium is loaded on SiO2A surface layer.
FIG. 4 shows Se3d on Se/SiO2XPS spectra on. As shown, a distinct peak appears around 55.2eV, which is attributed to elemental selenium. No peaks corresponding to other selenium oxidation states were observed on the XPS spectrum. This indicates the selenium precursor (Na)2SeO3) Completely reduced to elemental selenium.
FIG. 5 shows SiO2And Se/SiO2XRD diffraction pattern of the sample (2) shows SiO2The spectrum of the substance is consistent with the crystal faces 101, 102 and the like in the standard spectrum, and the substance is proved to be SiO2. From Se/SiO2The diffraction peaks of the selenium-enriched powder appear sharp peaks at 23 degrees and 29 degrees, and the peaks are characteristic peaks of elemental selenium, so that the reduced elemental selenium is successfully loaded on SiO2Above.
In order to discuss the mechanism of efficient mercury adsorption, an XPS method is adopted to research Se/SiO2The surface chemical reaction of (2). As shown in fig. 6, at 103.7eV, a well-resolved peak was observed in the Hg4f spectrum, which can be classified as HgSe. FIG. 7 shows Se/SiO2Se3 dpxs spectrum above. As shown in the figureShown in the formula (I) with fresh Se/SiO2In contrast, the binding energy of Se3d is shifted to lower regions. The values of the binding energy 54.2eV of Se3d and the transition of Se3d are consistent with FIG. 4.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of the high-efficiency mercury adsorbent for the exhaust gas liquid is characterized by comprising the following steps:
s1 selecting selenide powder, reductant powder and a solvent to mix them to form a mixed solution in which the selenide is reduced to form selenium;
s2, adding an adsorbent carrier into the mixed solution, and stirring to enable the selenium to be adsorbed on the adsorbent carrier;
s3 adding a PH adjusting agent to the mixed solution processed in step S2 to make the mixed solution alkaline, filtering the mixed solution, and drying the solid obtained by filtering to obtain the desired adsorbent.
2. The method for preparing the exhaust gas-liquid high-efficiency mercury adsorbent of claim 1, wherein in step S1, the selenide is selenate, selenite, or selenium dioxide.
3. The method for preparing the high-efficiency mercury sorbent for exhaust gas liquids as claimed in claim 2, wherein in step S1, the reducing agent is vitamin C, sodium borohydride, glutathione, hydrazine hydrate or lithium aluminum hydride.
4. The method of claim 3, wherein in step S1, the adsorbent support is spherical silica or gamma alumina microspheres.
5. The method of claim 4, wherein the particle size of the adsorbent is less than 100 μm.
6. The method for preparing the high-efficiency mercury sorbent for exhaust gas liquids as claimed in any one of claims 1 to 5, wherein in step S3, the adsorption efficiencies of the selenium-loaded mercury sorbent are all more than 90%.
7. The method for preparing the high-efficiency mercury sorbent for exhaust gas liquids as claimed in claim 1 or 2, wherein in step S3, the PH adjuster is sodium hydroxide solution.
8. The method for preparing the high-efficiency mercury sorbent for exhaust gas liquids as claimed in claim 1 or 2, wherein the drying temperature is 100 ℃ to 150 ℃ for 8h to 12h in step S3.
9. The method for preparing the high-efficiency mercury sorbent for exhaust gas liquids as claimed in claim 1 or 2, wherein in step S1, the solvent is deionized water.
10. A mercury sorbent obtained by the method of manufacture of any one of claims 1 to 9.
CN202111001778.0A 2021-08-30 2021-08-30 Preparation method and product of high-efficiency mercury adsorbent for waste gas liquid Pending CN113713757A (en)

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