NL2033523B1 - Method for preparing ceramic nano-mercury adsorption material modified by nano-selenium plasma - Google Patents
Method for preparing ceramic nano-mercury adsorption material modified by nano-selenium plasma Download PDFInfo
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- NL2033523B1 NL2033523B1 NL2033523A NL2033523A NL2033523B1 NL 2033523 B1 NL2033523 B1 NL 2033523B1 NL 2033523 A NL2033523 A NL 2033523A NL 2033523 A NL2033523 A NL 2033523A NL 2033523 B1 NL2033523 B1 NL 2033523B1
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- mercury
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- selenium
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 108
- 239000000463 material Substances 0.000 title claims abstract description 70
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 63
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 38
- 239000011669 selenium Substances 0.000 title claims abstract description 38
- 239000000919 ceramic Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 30
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000004888 barrier function Effects 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 229940091258 selenium supplement Drugs 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003546 flue gas Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 239000010802 sludge Substances 0.000 claims description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000012163 sequencing technique Methods 0.000 claims description 3
- 229960001471 sodium selenite Drugs 0.000 claims description 3
- 235000015921 sodium selenite Nutrition 0.000 claims description 3
- 239000011781 sodium selenite Substances 0.000 claims description 3
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical class [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 claims 1
- 150000002730 mercury Chemical class 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 7
- 239000002912 waste gas Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 229940041669 mercury Drugs 0.000 description 45
- 208000028659 discharge Diseases 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229960005196 titanium dioxide Drugs 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- 244000138502 Chenopodium bonus henricus Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001663154 Electron Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229960001841 potassium permanganate Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- B01J20/28014—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 form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28035—Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
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- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B01J20/3295—Coatings made of particles, nanoparticles, fibers, nanofibers
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B01D2253/302—Dimensions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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Abstract
The present invention discloses a method for preparing a ceramic nano—mercury adsorption material modified by a nano—selenium plasma, including: subjecting the ceramic nano—mercury adsorption material to plasma. modification. on. multiple adsorption. material layers by means of a dielectric barrier discharge at normal temperature and pressure to prepare the ceramic nano—mercury adsorption material modified by the nano—selenium plasma. A capacity for adsorption of the modified material, a specific surface area for adsorption, and mercury adsorption sites are increased, an advanced treatment of Hercury—containing waste gas and wastewater is further improved, and a regeneratable capacity of the material is increased, so that multiple regenerations can be realized, and the material costs can be reduced.
Description
METHOD FOR PREPARING CERAMIC NANO-MERCURY ADSORPTICN MATERIAL
MODIFIED BY NANO-SELENIUM PLASMA
The present invention relates to the technical field of mer- cury adsorption materials, and in particular, relates to a method for preparing a ceramic nano-mercury adsorption material modified by a nano-selenium plasma.
At present, a mercury-containing waste gas is mainly adsorbed and taken in. Adsorbents mainly include activated carbon, silver- loaded activated carbon, etc. Generally, the activated carbon has a problem of poor adsorption effect and it still belongs to haz- ardous waste after saturated adsorption, and the silver-loaded ac- tivated carbon has a problem of high cost and cannot be used on a large scale; absorption methods mainly include a potassium perman- ganate solution absorption, an iodine complex absorption method, a sodium sulfide + chlorine complex method, etc., but they are not used to achieve standard emissions. Mercury-containing wastewater is mainly treated by a sedimentation/flocculation method, an ad- sorption method, a membrane filtration method, an ion exchange method, a biological method, etc., which has the problems of poor treatment effect and high costs. The plasma can act as both a high heat source and chemically active particles, can directly acceler- ate the start of a reaction in the absence of a catalyst, and pro- vide enough energy for the reaction, which is a method for crack- ing natural gas with high efficiency and low energy consumption.
And compared with traditional processes, the plasma technology has the characteristics of flexible production scale, no pollution, removable catalyst, less investment, high conversion rate and rap- id reaction. Therefore, a method for preparing a ceramic nano- mercury adsorption material modified by a nano-selenium plasma is needed.
The present invention provides a method for preparing a ce- ramic nano-mercury adsorption material modified by a nano-selenium plasma with simple operations.
A method for preparing a ceramic nano-mercury adsorption ma- terial modified by a nano-selenium plasma of the present invention includes: subjecting the ceramic nano-mercury adsorption material to plasma modification on multiple adsorption material layers by means of a dielectric barrier discharge at normal temperature and pressure to prepare the ceramic nano-mercury adsorption material modified by the nano-selenium plasma.
Preferably, parameters for the dielectric barrier discharge are a voltage of 3-5 kV and a frequency of a pulse current of 20 kHz.
Preferably, the nano-selenium is obtained by reducing sodium selenite as a selenium source in an aerobic granular sludge reac- tor, a sludge concentration in the reactor is 3000 mg/L, a sludge volume index is 33.6 mL/g, and a sequencing batch granular sludge reactor 1s operated at 22-25°C and near neutral pH.
Preferably, a mixed gas composed of helium gas and methane gas in a volume ratio of 7: 13 is introduced into a closed cavity of a dielectric barrier discharge plasma reactor, a flow rate of the mixed gas is 2 L/min, and then a current is applied to the di- electric barrier discharge plasma reactor through a pulse power supply device and maintained for 5-30 minutes.
A ceramic nano-mercury adsorption material modified by a nano-selenium plasma includes: a first adsorption material layer, a second adsorption material layer, and a third adsorption materi- al layer, wherein the first adsorption material layer, the second adsorption material layer and the third adsorption material layer are sequentially stacked. The first adsorption material layer has a saturated Hg** capacity for adsorption of 3.6 mg/g, a specific surface area for adsorption of is 128 m“/g, and a mercury emission concentration in flue gas is less than 0.01 mg/m’; the second ad- sorption material layer has a saturated Hg" capacity for adsorption of 6 mg/g, a specific surface area for adsorption of 120 m?/g, and the mercury emission concentration in the flue gas is less than
0.01 mg/m’; and the third adsorption material layer has a saturated
Hg"! capacity for adsorption of 5 mg/g, a specific surface area for adsorption of 180 m?/g, and is regeneratable for at least 5 times, and the mercury emission concentration in the flue gas is less than 0.01 mg/m’.
Use of a ceramic nano-mercury adsorption material modified by a nano-selenium plasma in mercury removal includes: introducing a mercury-containing gas into a reactor filled with the ceramic nano-mercury adsorption material modified by the nano-selenium plasma for removal of mercury at 60-90°C.
The present invention has the following beneficial effects.
A capacity for adsorption of the modified material, a specif- ic surface area for adsorption, and mercury adsorption sites are increased, an advanced treatment of mercury-containing waste gas and wastewater is further improved, and a regeneratable capacity of the material is increased, so that multiple regenerations can be realized, and the material costs can be correspondingly re- duced.
The principles and features of the present invention are de- scribed below, and the examples are only used to explain the pre- sent invention, but not to limit the scope of the present inven- tion.
In the present example: a method for preparing a ceramic nano-mercury adsorption ma- terial modified by a nano-selenium plasma includes: subjecting the ceramic nano-mercury adsorption material to plasma modification on multiple adsorption material layers by means of a dielectric bar- rier discharge at normal temperature and pressure to prepare the ceramic nano-mercury adsorption material modified by the nano- selenium plasma, parameters for the dielectric barrier discharge are a voltage of 4 kV and a frequency of a pulse current of 20 kHz, and a mixed gas composed of helium gas and methane gas in a volume ratio of 7: 13 is introduced into a closed cavity of a die- lectric barrier discharge plasma reactor, a flow rate of the mixed gas is 2 L/min, and then a current is applied to the dielectric barrier discharge plasma reactor through a pulse power supply de- vice and maintained for 5-30 minutes.
The nano-selenium is obtained by reducing sodium selenite as a selenium source in an aerobic granular sludge reactor, a sludge concentration in the reactor is 3000 mg/L, a sludge volume index is 33.6 mL/g, and a sequencing batch granular sludge reactor is operated at 22-25°C and near neutral pH.
The plasma can realize material modification. A mercury ion imprinted material has a mercury capacity for adsorption reaching 36579 ug/g, and a ceramic nano-adsorption material has a saturated
Hg** capacity for adsorption of 5 mg/g, and is regeneratable for at least 5 times. In order to further improve an adsorption effect of mercury, and realize an advanced purification and standard emis- sions of mercury in mercury-containing waste gas and wastewater, key parameters such as plasma voltage, current and frequency are adjusted to realize nano-selenium modification on material, make full use of a high affinity of mercury to selenium, and improve an adsorption capacity of the material for mercury.
The material is subjected to modifying by a low-temperature plasma, the energy of electrons and ions can reach more than 10 eV, and a treatment temperature is normal temperature. The low- temperature plasma is applicable to surface polymerization, sur- face grafting, metallurgy, surface catalysis, chemical synthesis and surface modification of various powders, particles and sheets.
Low-temperature plasma parameters
VO Ga aa
Maximum discharge W (2000 Pa} 150 180 me
Towa [oe [een
ET Lc
Gap between two mm 5-80 10-70 ea
Example 1: a ceramic nanotube is selected as a catalytic sup-
port: an adsorption material layer has a saturated Hg’ capacity for adsorption of 3.6 mg/g and a specific surface area for adsorp- tion of 128 m°/g, and is regeneratable for at least 3 times, and a mercury emission concentration in flue gas is less than 0.01 mg/m’, 5 and is applicable to the adsorption of Hg?’ in water body.
Example 2: a carbon nanotube is selected as a catalytic sup- port: an adsorption material layer has a saturated Hg? capacity for adsorption of 6 mg/g and a specific surface area for adsorption of 120 mè/g, and is regeneratable for at least 4 times, and the mercu- ry emission concentration in the flue gas is less than 0.01 mg/m’.
Example 3: a nano-selenium tube is selected as a catalytic support: an adsorption material layer has a saturated Hg** capacity for adsorption of 5 mg/g and a specific surface area for adsorp- tion of 180 m°/g, and is regeneratable for at least 5 times, and the mercury emission concentration in the flue gas is less than 0.01 mg/m’, and is applicable to the adsorption of Hg" in the wa- ter body.
Through Examples 1-3, the adsorption rate of nano-selenium is very fast in first two hours of the adsorption reaction, the ad- sorption capacity increases rapidly and about half of cadmium ions are adsorbed and removed in 15 minutes. In the following 6 hours, the adsorption capacity is still gradually increasing, but the rate of increase is much less than the first two hours. The whole adsorption reaction reaches adsorption equilibrium at 8 hours, and the adsorption capacity is 32.2 mg/g at this time. To ensure that the reaction reaches adsorption equilibrium, the reaction time of subsequent adsorption experiments is set at 10 hours. In the ini- tial stage of the reaction, the adsorption rate is very fast be- cause of high concentration of the cadmium ions in solution and there are sufficient active sites on the nano-selenium, so that the cadmium ions can be rapidly adsorbed to the sites; as the re- action proceeds, there are fewer and fewer active sites on adsor- bents, which leads to the difficulty of adsorption and binding of the cadmium ions. Furthermore, at the end of the reaction, the whole system reaches adsorption-desorption equilibrium, and the cadmium ion content reaches equilibrium in the solid-liquid phase.
According to adsorption isotherm data, an enthalpy change
(AHo), an entropy change (Aso) and a Gibbs free energy change (AGo) of the adsorption process can be obtained. When AGo < 0, it indicates that the adsorption process of u{vI) on PTFG. 4 is spon- taneous, and its value becomes gradually decreases with the in- crease of temperature, which indicates that the increase of tem- perature is beneficial to the adsorption of u(vI). In addition, when AHo > 0, it indicates that the removal process of u(vI) by
PTFG. 4 is endothermic, and the increase of temperature can in- crease the degree of endothermic reaction, which is consistent with the isotherm experimental results. This may be because when u(vI) reaches the adsorbent surface in the form of hydrated ions, u{vI)} needs energy to remove these bound water molecules, while the required energy is much higher than that released by the reac- tion of u(vI) with functional groups on the surface of the materi- al, so the removal process of u(vI) by PTFG-4 is endothermic. Fur- thermore, when ASo > 0, it indicates that the adsorption process is driven by entropy, which indicates that when u(vI) is adsorbed to the surface of PTFG.4, the degree of freedom of solid-liquid interface increases, therefore the adsorption process is a sponta- neous endothermic process.
Nano-selenium has a strong mercury affinity property. Com- pared with sulfur, selenium has a higher affinity to mercury with an equilibrium constant of 1045, which is one million times that of sulfur to mercury, at the same time, red selenium has a strong activity characteristic of nano-structure, therefore, the applica- tion of the red selenium in the prevention and control of mercury pollution has a great application prospect.
In a cold plasma device, a specific electrode is arranged in a sealed container to form an electric field, and the distance be- tween molecules and the free movement distance of the molecules or ions becomes longer and longer, and they collide under the action of the electric field to form a plasma; because glow will be emit- ted at this time, it is called glow discharge. The gas pressure during glow discharge has a great influence on the material treat- ment effect, and other influencing factors include discharge pow- er, gas composition, material type, etc. The power supply is used as a main component of a plasma generating device, the power range is generally between 50-500 W, and according to the difference in frequency of power supply, the power supply can be divided into direct current, low frequency (50 Hz-50 kHz) and radio frequency (designated frequency 13.56 MHz) microwave (commonly 2450 MHz).
The nano-modified ceramic mercury adsorbed particles have a specific surface area effect and a small size effect, and can be used as a common catalytic support. A unique hollow tubular struc- ture with a large aspect ratio of ceramic shows special surface effect and electronic effect, which are favorable aspects of good catalyst supports. Selecting the ceramic nanotubes as the catalyst support 161’ can greatly improve the activity and selectivity of the catalyst, and the diffusion rate of most gases through the ce- ramic nanotubes is very fast, which is thousands of times that of conventional catalyst granular.
The plasma is a partially ionized gas, the system mainly con- sists of charged particles (electrons, positive ions, negative ions, etc.), under the influence of an external electric field, a magnetic field, and an electromagnetic field, there is a variety of elementary reactions in the plasma discharge process, which have unique physical properties such as electricity, light and heat, and can be used to modify the surface of the material. The parameter ranges of these particle energies are as follows: elec- trons 0-20 ev, metastable particles 0-2 ev, ions 0.03-0.05 ev, and photons 3-40 ev. In the process of treating the material surface with the plasma, high velocity electrons can ionize, excite, or break the reacted molecules into free radical fragments. Positive ions and some neutral atoms that can combine with some molecules on the surface of the material have a certain etching effect on the surface of the material, and some neutral atoms and free radi- cals will deposit on the surface of the material to form a deposi- tion layer.
In the dielectric barrier discharge plasma reactor, hydrogen gas is excited by high-energy electrons and an electric field in an argon atmosphere and converted into an excited state as an electron donor, and a ceramic receives electrons provided by the hydrogen gas in the excited state under the action of the plasma, so that the valence state is reduced to be converted into a Mag-
neli state (titanium oxide with a low valence state, namely, Ti-
Ox). Unlike the ceramic in a normal state, the Magneli-state tita- nium oxide formed after dielectric barrier discharge treatment has lower valence state, so it has a smaller band gap (2.6 eV), and thus has the performance of absorbing visible light. In addition, the high-energy electrons produced by the dielectric barrier dis- charge can purify impurities in the ceramic material and modify surface structure of the ceramic material, which eventually leads to more pore structures and larger specific surface areas of the nano-ceramics, thus being beneficial to the efficient photocataly- sis of the modified ceramic.
A capacity for adsorption of the modified material, a specif- ic surface area, and mercury adsorption sites are increased, an advanced treatment of mercury-containing waste gas and wastewater is further improved, and a regeneratable capacity of the material is increased, so that the material is regeneratable for 8 times, and the material costs can be correspondingly reduced.
Before modification, the ceramic nano-material has the satu- rated Hg** capacity for adsorption of 3.6 mg/g and the specific surface area for adsorption of 128 m‘/g, and is regeneratable for at least 5 times and applicable to removal of mercury from the flue gas and the water body; a molecular imprinting material has the saturated Hg’ capacity for adsorption of 6.0 mg/g and the spe- cific surface area for adsorption of 120 m‘/g, and is regeneratable for at least 4 times and applicable to removal of mercury from the flue gas; and the activated carbon adsorption material has the saturated Hg capacity for adsorption of 1.0 mg/g and the specific surface area for adsorption of 180 m‘/g, and is applicable to re- moval of mercury from the flue gas and the water body.
After modification, the ceramic nano-material has the satu- rated Hg“ capacity for adsorption of 4.8 mg/g and the specific surface area for adsorption of 140 m°/g, and is regeneratable for at least 5 times and applicable to removal of mercury from the flue gas and the water body; the molecular imprinting material has the saturated Hg? capacity for adsorption of 7.2 mg/g and the spe- cific surface area for adsorption of 130 m‘/g, and is regeneratable for at least 5 times and applicable to removal of mercury from the flue gas; and the activated carbon adsorption material has the saturated Hg capacity for adsorption of 1.3 mg/g and the specific surface area for adsorption of 210 m’/g, and is applicable to re- moval of mercury from the flue gas and the water body.
The above are only the preferred examples of the present in- vention, but the scope of protection of the present invention is not limited to this, any equivalent substitution or change made by a person skilled in the technical field within the technical scope disclosed by the present invention according to the technical scheme of the present invention and its inventive concept shall fall within the scope of protecticn of the present invention.
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