CN110665455A - Mercury removing adsorbent with core-shell structure and preparation method thereof - Google Patents
Mercury removing adsorbent with core-shell structure and preparation method thereof Download PDFInfo
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- CN110665455A CN110665455A CN201911012730.2A CN201911012730A CN110665455A CN 110665455 A CN110665455 A CN 110665455A CN 201911012730 A CN201911012730 A CN 201911012730A CN 110665455 A CN110665455 A CN 110665455A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 45
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 43
- 239000011258 core-shell material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims abstract description 10
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 10
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- 239000002114 nanocomposite Substances 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000000969 carrier Substances 0.000 claims abstract description 3
- 239000002594 sorbent Substances 0.000 claims abstract 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 5
- 239000002122 magnetic nanoparticle Substances 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011011 black crystal Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
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- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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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
-
- 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
- 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
- B01D53/86—Catalytic processes
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a mercury removal adsorbent with a core-shell structure, which is characterized in that the mercury removal adsorbent is made of Fe3O4The nanoparticles are used as carriers through reaction of Fe3O4Surface in-situ growth MoS2Nanosheet, forming Fe3O4@MoS2Core-shell structure to obtain a core-shell structured polymerA mercury sorbent. In the invention, Fe3O4Dispersing the nano particles serving as a raw material into deionized water, adding ammonium molybdate tetrahydrate and thiourea, and preparing a mercury removal adsorbent, namely MoS, by using a hydrothermal method2@Fe3O4The nano composite material has good crystallinity, controllable appearance and size and good adsorption performance.
Description
Technical Field
The invention belongs to the field of mercury removal materials, and particularly relates to a mercury removal adsorbent with a core-shell structure and a preparation method thereof.
Background
Molybdenum disulfide, metallic luster, black powder, a hexagonal system and a layered structure. The molybdenum disulfide and the graphene have similar structures and performances, only weak van der waals force exists between layers, the bonding energy is very low, the layers are easy to separate, and the friction factor is very low. Molybdenum disulfide has good heat resistance and stable chemical properties, is insoluble in dilute acid and water, but is soluble in aqua regia and hot concentrated sulfuric acid. Due to these characteristics, molybdenum disulfide (MoS2) has an energy band gap with an adjustable size, and thus has attracted much attention as a high-tech material in recent years, and is widely used in the fields of photoelectric devices, mechanical lubrication, catalysis, semiconductor materials, and the like. Compared with common molybdenum disulfide, the nano molybdenum disulfide has more excellent performance and plays an important role in the fields of aerospace, military and the like. The nano-grade molybdenum disulfide has larger specific surface area, is easier to adsorb gas particles, has higher sensitivity to light and gas, and is also applied to the aspect of detection. Molybdenum disulfide, however, has poor conductivity, which also limits its applications.
The magnetic nano-particles are novel nano-functions, have good biocompatibility and special magnetic functions, are mainly used for adsorbing heavy metal ions and organic pollutants in the environment, the composite material obtained by attaching peroxidase to the surface of the magnetic nano-particles has the advantages of the magnetic nano-particles and the catalytic activity of the enzyme, can be used for biocatalysis and bioseparation, and various composite structures of various substances can endow the composite material with various characteristics, so that the magnetic nano-particles have wide application fields. Along with the wide application of nano magnetic materials in various fieldsUsed as an important magnetic material-nano Fe3O4The particles have small particle size, high specific surface area, magnetism and permanent agglomeration. And the preparation process is nontoxic and non-dangerous.
Ferroferric oxide, chemical formula Fe3O4. The black iron oxide is also called magnetic iron oxide because it is a black crystal having magnetism, and can be approximately regarded as a compound composed of ferrous oxide and iron oxide (FeO. Fe)2O3). The substance is soluble in acid solution, and insoluble in water, alkali solution, and organic solvent such as ethanol and diethyl ether. The natural ferroferric oxide is insoluble in acid solution and is easily oxidized in air in a wet state. Fe3O4The nano-particles are magnetic black crystals, are small in size and large in specific surface area, have poor surface smoothness and can increase the contact surface of chemical reaction.
In recent years, a great deal of research shows that the nano material has no remarkable high efficiency for removing typical toxic pollution. Nano Fe3O4As functional materials, many special functions are exhibited in terms of magnetic recording materials, special catalytic materials, basic materials for magnetic fluids, and the like, but since Fe3O4The mutual attraction between the magnetic nano particle dipoles leads the nano particles to be easy to agglomerate, the surface of the nano particles is modified, the dispersibility of the nano particles and the stability of colloid of the nano particles can be improved, and a new function is introduced. The magnetic composite adsorbent is prepared by introducing the magnetic oxide into the adsorbent, and the rapid separation can be realized by using an external magnetic field.
Disclosure of Invention
The invention aims to provide a novel, efficient and recyclable mercury removal adsorbent with a core-shell structure and a preparation method thereof.
In order to achieve the purpose, the invention provides a mercury removal adsorbent with a core-shell structure, which is characterized in that the mercury removal adsorbent with the core-shell structure is made of Fe3O4The nanoparticles are used as carriers through reaction of Fe3O4Surface in-situ growth MoS2Nanosheet, forming Fe3O4@MoS2And (4) obtaining the mercury removal adsorbent with the core-shell structure by the core-shell structure.
The invention also provides a preparation method of the mercury removal adsorbent with the core-shell structure, which is characterized by comprising the following steps:
step 1: mixing ammonium molybdate tetrahydrate [ (NH)4)6Mo7O24·4H2O]Adding thiourea into deionized water, and stirring for dissolving to obtain a solution A;
step 2: mixing Fe3O4Dispersing the nano particles into the solution A, and uniformly stirring to obtain a solution B;
and step 3: pouring the solution B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 10 hours at 160-200 ℃ to enable Fe3O4MoS deposition on surface of nanoparticles2Nanosheet, naturally cooling, washing and drying to obtain the mercury removal adsorbent with the core-shell structure, namely MoS2@Fe3O4A nanocomposite material.
Preferably, in the step 1, the concentration of ammonium molybdate tetrahydrate in the solution A is 0.024-0.028 mol/L, the concentration of thiourea is 0.833-1 mol/L, and the molar ratio of ammonium molybdate tetrahydrate to thiourea is not more than 0.0283: 1.
Preferably, in the step 2, the concentration of ammonium molybdate tetrahydrate in the solution B is 0.024-0.028 mol/L, the concentration of thiourea is 0.833-1 mol/L, and Fe3O4The concentration of the nano particles is 0.0072-0.0086 mol/L.
Preferably, Fe in said step 23O4The preparation of the nano-particles comprises: FeCl is added3·6H2O dissolved in pure ethylene glycol solution (concentration)>99%), stirring and dissolving by using a magnetic stirrer, sequentially adding anhydrous sodium acetate and polyethylene glycol, magnetically stirring for 60-90 min, transferring to a reaction kettle, reacting for 8h at 200 ℃, cooling to room temperature, repeatedly washing for 3-5 times by using deionized water and anhydrous ethanol respectively, placing in a drying oven, and drying at 60 ℃ to obtain Fe3O4And (3) nanoparticles.
Preferably, the washing in step 3 specifically comprises: washing with deionized water and anhydrous ethanol respectively in 7000r/min high speed centrifuge for 3-6 times, each for 3 min.
According to the invention, Fe3O4 is used as a raw material, a MoS2/Fe3O4 nano composite material is synthesized by a hydrothermal method, in-situ coating of MoS2 on Fe3O4 is realized, Fe3O4 is used as a carrier, and a catalyst adsorbent is coated on the surface of particles, so that the mercury removal adsorbent with a core-shell structure is prepared.
The mercury removal adsorbent with the core-shell structure has MoS2@Fe3O4Core-shell structure of Fe3O4@MoS2The core-shell structure has very positive chemical effect, Fe3O4Has certain magnetism, so that MoS generated on the surface2Condensed in Fe3O4Surface of nanoparticles, MoS2Is itself of graphene-like structure, Fe3O4The mercury adsorbent also has a larger specific surface area, and is beneficial to the adsorption of elemental mercury. Iron oxide has a large specific surface area and intrinsic magnetism, and is easy to cause a spontaneous aggregation phenomenon. The prepared MoS2/Fe3O4 nano-particle has good crystallinity, controllable morphology and size and good catalytic and adsorption properties.
Compared with the prior art, the invention has the beneficial effects that:
(1) the adsorbent for demercuration and the recovery method thereof provided by the invention have the advantages of simple and controllable process and mild operation conditions, and the demercuration efficiency of the obtained demercuration adsorbing material in a nitrogen atmosphere is very high.
(2) The demercuration adsorbent can be used for demercuration of flue gas of a power plant and can also be used for adsorbing mercury exposed to the atmospheric environment at ordinary times, and the mercury can be sprayed by adopting a method of spraying activated carbon by the power plant, and Fe3O4The adsorbent is a matrix, and the adsorbent saturated in adsorption can be partially recovered by a magnet, and can be reused after being desorbed after recovery.
(3) The demercuration adsorbent prepared by the invention has MoS2@Fe3O4The core-shell structure is easy to prepare due to the special structure and magnetism, and can be partially recycled by utilizing a magnetThe mercury removing adsorbent is environment-friendly and economical, has high efficiency, is an ideal mercury removing adsorbent and has good application prospect.
Drawings
Fig. 1 is an SEM image of demercuration adsorbent 1 prepared in example 1 of the present invention;
fig. 2 is an SEM image of the demercuration adsorbent 2 prepared in example 2 of the present invention;
fig. 3 is an SEM image of the demercuration adsorbent 3 prepared in example 3 of the present invention;
FIGS. 4 to 6 are mercury concentration change curves of the demercuration adsorbents 1, 2 and 3 prepared in the embodiments 1 to 3 of the present invention in a demercuration adsorption experiment;
FIG. 7 shows a reaction platform for mercury adsorption experiments in flue gas using a fixed bed according to the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The invention adopts a fixed bed as a reaction platform of a flue gas mercury adsorption experiment, and the capability of the composite material for removing mercury is researched by referring to fig. 7. N at a constant flow rate2The mercury generator mixes the mercury vapor with a certain concentration and the protective gas nitrogen in the gas mixing valve. In order to keep the system stable, the mixed gas firstly passes through a bypass and then passes through a mercury analyzer, and finally the gas is recovered after being treated by a tail gas treatment device. When the mercury source signal is stable and the temperature controller maintains the reaction temperature at 120 ℃, the gas path is cut to the main path, the mixed gas starts to react with the adsorbent fixed by quartz cotton and quartz beads through the quartz tube, and the content of mercury in the mixed gas is measured and recorded for 2 hours.
Example 1
The embodiment provides a preparation method of a mercury removal adsorbent with a core-shell structure, which comprises the following specific steps:
step 1: 1.35g of FeCl3·6H2O dissolved in 40mL of pure ethylene glycol solution (concentration)>99 percent), stirring for 30min by using a magnetic stirrer, sequentially adding 3.6g of anhydrous sodium acetate and 1.0g of polyethylene glycol, and magnetically stirring for 60-90 min at the rotating speed of 5 r/min; transferring the obtained solution to a 100ml water reaction kettle, reacting for 8 hours at 200 ℃, cooling to room temperature after the reaction is finished, repeatedly washing for 3-5 times by using absolute ethyl alcohol and deionized water, and washing the washed Fe3O4The nano particles are put into an oven and dried at the temperature of 60 ℃ to obtain clean Fe3O4A nanoparticle;
step 2: 1.75g of ammonium molybdate tetrahydrate [ (NH4)6Mo7O24·4H2O]Adding 3.8g of thiourea into 50mL of deionized water, and stirring for 30min by using a magnetic stirrer at the rotating speed of 5r/min to obtain a solution A;
and step 3: 0.1g of Fe obtained in step 13O4Dispersing the nano particles into the solution A prepared in the step 2, and stirring for 30min by using a magnetic stirrer at the rotating speed of 5r/min to obtain a solution B;
and 4, step 4: pouring the solution B obtained in the step 3 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 10 hours at 160 ℃ to enable Fe3O4MoS deposited on surface of nano-particles2Naturally cooling the nano-sheets, centrifugally washing the nano-sheets for 3-6 times in a 7000r/min high-speed centrifuge by using deionized water and absolute ethyl alcohol for 3min each time, and finally drying the cleaned samples in a 60 ℃ drying oven for 10h to obtain a mercury removal adsorbent 1, namely MoS2@Fe3O4A nanocomposite material.
Example 2
The difference between the example and the example 1 is that the hydrothermal reaction temperature in the step 4 is 180 ℃, the rest steps are the same as the example 1, and finally the mercury-removing adsorbent 2 is obtained.
Example 3
The difference between this example and example 1 is that the hydrothermal reaction temperature in step 4 is 200 ℃, the rest steps are the same as example 1, and finally mercury-removing adsorbent 3 is obtained.
As shown in FIGS. 1, 2 and 3, the temperature of synthesis is variedElevation of (3), Fe3O4The surface of the nano particle is coated with more MoS2Nanosheets, MoS2The crystallinity and order of the nanoplatelets also increase.
As shown in figures 4, 5 and 6, the smoke of a simulated power plant (120 ℃) is treated by N2As a carrier gas, the demercuration rates of the mercury removal adsorbent 1 and the mercury removal adsorbent 2 can almost reach 100% within 50min, the demercuration rate of the mercury removal adsorbent 3 is 98-100%, the demercuration rates are stable, the demercuration rate of molybdenum disulfide produced by the process can only reach about 80%, and the demercuration effect of the invention is far better than that of industrial molybdenum disulfide.
Claims (6)
1. The mercury removal adsorbent with the core-shell structure is characterized in that the mercury removal adsorbent is made of Fe3O4The nanoparticles are used as carriers through reaction of Fe3O4Surface in-situ growth MoS2Nanosheet, forming Fe3O4And the @ MoS2 core-shell structure is adopted to obtain the mercury removal adsorbent with the core-shell structure.
2. The preparation method of the mercury removal adsorbent with the core-shell structure, which is described in claim 1, is characterized by comprising the following steps:
step 1: adding ammonium molybdate tetrahydrate and thiourea into deionized water, and stirring for dissolving to obtain a solution A;
step 2: mixing Fe3O4Dispersing the nano particles into the solution A, and uniformly stirring to obtain a solution B;
and step 3: pouring the solution B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 10 hours at 160-200 ℃ to enable Fe3O4MoS deposition on surface of nanoparticles2Nanosheet, naturally cooling, washing and drying to obtain the mercury removal adsorbent with the core-shell structure, namely MoS2@Fe3O4A nanocomposite material.
3. The method for preparing the mercury removal adsorbent with the core-shell structure according to claim 2, wherein in the step 1, the concentration of ammonium molybdate tetrahydrate in the solution A is 0.024-0.028 mol/L, the concentration of thiourea is 0.833-1 mol/L, and the molar ratio of ammonium molybdate tetrahydrate to thiourea is not more than 0.0283: 1.
4. the method for preparing the mercury removal adsorbent with the core-shell structure according to claim 2, wherein in the step 2, the concentration of ammonium molybdate tetrahydrate in the solution B is 0.024-0.028 mol/L, the concentration of thiourea is 0.833-1 mol/L, and Fe3O4The concentration of the nano particles is 0.0072-0.0086 mol/L.
5. The method for preparing mercury removal sorbent with core-shell structure according to claim 2, wherein in the step 2, Fe3O4The preparation of the nano-particles comprises: FeCl is added3·6H2Dissolving O in a pure ethylene glycol solution, stirring and dissolving by using a magnetic stirrer, sequentially adding anhydrous sodium acetate and polyethylene glycol, magnetically stirring for 60-90 min, transferring to a reaction kettle, reacting for 8h at 200 ℃, cooling to room temperature, repeatedly washing with deionized water and anhydrous ethanol for 3-5 times respectively, placing in an oven, and drying at 60 ℃ to obtain Fe3O4And (3) nanoparticles.
6. The method for preparing the mercury removal adsorbent with the core-shell structure according to claim 2, wherein the washing in the step 3 specifically comprises: and respectively carrying out centrifugal washing for 3-6 times and 3min each time by using deionized water and absolute ethyl alcohol in a 7000r/min high-speed centrifuge.
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