CN105688951A - Preparation method of copper and cerium composite silver halide/silver photocatalyst and flue gas demercuration method adopting photocatalyst - Google Patents
Preparation method of copper and cerium composite silver halide/silver photocatalyst and flue gas demercuration method adopting photocatalyst Download PDFInfo
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- CN105688951A CN105688951A CN201610043850.9A CN201610043850A CN105688951A CN 105688951 A CN105688951 A CN 105688951A CN 201610043850 A CN201610043850 A CN 201610043850A CN 105688951 A CN105688951 A CN 105688951A
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- silver halide
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 99
- 239000004332 silver Substances 0.000 title claims abstract description 99
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003546 flue gas Substances 0.000 title claims abstract description 56
- -1 silver halide Chemical class 0.000 title claims abstract description 54
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000010949 copper Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title abstract 8
- 239000002131 composite material Substances 0.000 title abstract 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 21
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 16
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 14
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- 239000001103 potassium chloride Substances 0.000 claims abstract description 4
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 50
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000013019 agitation Methods 0.000 claims description 23
- 229910002651 NO3 Inorganic materials 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- 239000003517 fume Substances 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 238000000227 grinding Methods 0.000 abstract 2
- 238000007873 sieving Methods 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 2
- 238000012258 culturing Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000000779 smoke Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 7
- 230000008030 elimination Effects 0.000 description 7
- 238000003379 elimination reaction Methods 0.000 description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 6
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- 244000138502 Chenopodium bonus henricus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- YFDLHELOZYVNJE-UHFFFAOYSA-L mercury diiodide Chemical compound I[Hg]I YFDLHELOZYVNJE-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/104—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
Abstract
The invention provides a preparation method of a copper and cerium composite silver halide/silver photocatalyst. The preparation method of the copper and cerium composite silver halide/silver photocatalyst comprises the following steps of mixing a ready Ce(NO3)3 solution with a Cu(NO3)2 solution, and then adding citric acid into an obtained first mixture, and heating insolating, grinding and sieving an obtained second mixture in sequence to obtain solid powder CuyCe1-yOz; adding the solid powder CuyCe1-yOz into an AgNO3 solution to obtain a solution A, and then adding a Na2CO3 solution into the solution A; afterwards, adding 0.1 mol of potassium chloride (KCl), potassium bromide (KBr) or potassium iodide (KI) into an obtained third mixture to obtain a solution B; culturing the solution B through a heating device, and then adding ethanediol into the cultured solution B to obtain a solution C; washing, drying, grinding and sieving the solution C to obtain the copper and cerium composite silver halide/silver photocatalyst. A flue gas demercuration method adopting the copper and cerium composite silver halide/silver photocatalyst comprises the following steps of making reaction liquid containing a copper and cerium codoped silver halide/silver photocatalyst; irradiating the reaction liquid and a mercury-containing flue gas by visible light to carry out demercuration. The preparation method of the copper and cerium composite silver halide/silver photocatalyst and the flue gas demercuration method adopting the copper and cerium composite silver halide/silver photocatalyst have the characteristics of good demercuration effect, low cost and the like, and can be widely applied to the field of atmospheric controlling.
Description
Technical field
The present invention relates to pollutant Prevention Technique, particularly relate to a kind of copper cerium compound silver halide/silver photocatalyst preparation method and adopt the flue gas hydrargyrum-removing method of this catalyst。
Background technology
Photocatalysis is increasingly subject to the attention of researcher as a green environmental protection technique, and it has important application prospect in energy regeneration and environmental improvement。Owing to semi-conducting material can produce electronics and the hole with relatively Strong oxdiative reducing power, to be therefore often used as catalysis material under the exciting of light。But, it is compared to semi-conducting material, sensitive material silver halide AgX has better photocatalysis effect: AgX is easier to absorb the electron hole pair that photon produces, and, the nanoparticle such as precious metals ag, Au has surface plasmon resonance effect, has higher absorbability in visible-range。Here, X represents halogen element Cl, Br or I。
The existence form of Mercury In Coal Combustion Flue Gas mainly has three kinds: Elemental Mercury Hg0, bivalent mercury Hg2+With particle mercury Hgp。The removal methods of hydrargyrum mainly has three kinds: the first is absorption method, and it adopts the Adsorption of Mercuries such as activated carbon, but because of its absorbability thus cannot use for a long time, and price also costly, affect flying dust commercial value；The second is catalytic oxidation, i.e. metal-oxide and HCl or O2In conjunction with by Elemental Mercury Hg0It is catalytically oxidized to bivalent mercury Hg2+Rear absorbed liquid removes, but owing to the method needs additionally to add mercury removal device, therefore the operating cost of coal fired power plant can be increased, the placement of catalyst is also a problem needing solution badly simultaneously；The third method is to adopt Conventional pollution elimination equipment, and it is by wet desulphurization and dust arrester elimination bivalent mercury Hg2+With particle mercury Hgp, but the method is to Hg0Removal effect very micro-。
As can be seen here, in the prior art, there is the problem that demercuration effect is poor or relatively costly in flue gas hydrargyrum-removing method。
Summary of the invention
In view of this, offer a kind of copper cerium compound silver halide/silver photocatalyst preparation method that a kind of demercuration is effective, cost is low is provided and adopts the flue gas hydrargyrum-removing method of this catalyst。
In order to achieve the above object, the method for preparing catalyst technical scheme that the present invention proposes is:
A kind of copper cerium compound silver halide/silver photocatalyst preparation method, comprises the steps:
Step 1, respectively by the cerous nitrate Ce (NO of certain mole3)3, copper nitrate Cu (NO3)2Stirring after being dissolved in deionized water, correspondence obtains Ce (NO3)3Solution, Cu (NO3)2Solution。
Step 2, under magnetic agitation mode, by Ce (NO3)3Solution adds Cu (NO3)2After in solution, continuing magnetic force stirs 20 minutes, obtains the first mixed solution；Afterwards, in the first mixed solution add citric acid, and successively magnetic agitation 30 minutes, stand 24 hours, obtain the second mixed solution；Wherein, add that the Citric Acid Dosage in the first mixed solution is copper nitrate and cerous nitrate mole sum 1～2 times。
Step 3, the second mixed solution is positioned in the water-bath of 70～80 DEG C and heats after 6～12 hours, be placed under sunlight and be exposed to the sun to dry state, this dry state sample is ground and is sized to more than 120 orders, obtains pressed powder CuyCe1-yOz；Wherein, y=0.05～0.3, z is that Ce and Cu forms the molal quantity of requisite oxygen during steady oxide。
Step 4, the silver nitrate of 0.1 mole is dissolved in a certain amount of deionized water after stir, obtain AgNO3Solution。
Step 5, by pressed powder CuyCe1-yOzAdd AgNO3In solution, also magnetic agitation, after 30 minutes, obtains solution A。
Step 6, by the Na of 0.1 mole2CO3After being dissolved in a certain amount of deionized water and stirring, obtain Na2CO3Solution。
Step 7, by Na2CO3Solution adds in solution A and magnetic agitation is after 20 minutes, adds potassium chloride (KCl), the potassium bromide KBr or potassium iodide KI of 0.1 mole, continues magnetic agitation 30 minutes, obtains B solution。
Step 8, B solution is placed in 50～80 DEG C of water bath heating devices under magnetic agitation mode and cultivates after 20 minutes, add the ethylene glycol of 10～25mL, continue to adopt magnetic means to stand 12～20 hours after stirring 20 minutes in condition of water bath heating, obtain C solution。
Step 9, employing deionized water are to, after C solution washing to neutrality, being placed in the baking oven of 60～80 DEG C dry 24 hours, and ground, be sized to more than 120 orders by dried object, obtain copper cerium compound silver halide/silver photocatalyst Ag/AgX/CuyCe1-yOz；Wherein, X is Cl, Br or I。
In sum, in copper cerium compound silver halide/silver photocatalyst preparation method of the present invention, the ceria CeO that will there is the strong absorbability in broadband but visible ray is hardly picked up2, copper oxide CuO and silver halide AgX compound, the transfer of semiconductor conduction band electronics and valence band hole can be promoted, strengthen efficiently separating of photo-generate electron-hole pair, strengthen the photocatalytic activity of obtained copper cerium compound silver halide/silver photocatalyst。It addition, ceria CeO2, nano cupric oxide CuO be of many uses but cheap common materials, therefore obtained copper cerium compound silver halide/silver photocatalyst cost also decreases。
In order to achieve the above object, the flue gas hydrargyrum-removing method technical scheme that the present invention proposes is:
A kind of flue gas hydrargyrum-removing method adopting copper cerium compound silver halide/silver photocatalyst, comprises the steps:
Step J, by copper cerium codope silver halide/silver photocatalyst Ag/AgX/CuyCe1-yOzIt is mixed and made into reactant liquor in the ratio of 1～5 g/l with water。
Step K, by the reactant liquor contacted with each other in radiation of visible light quartz glass class mercury removal device and mercury fume, strong oxidizing property hydroxyl radical free radical OH, the superoxide radical O of reactant liquor release2 -, hole h+Or Cl2/Br2/I2With the Hg in mercury fume0After there is oxidation reaction, the clean flue gas obtained is discharged into air。
In sum, in the flue gas hydrargyrum-removing method of employing copper cerium compound silver halide/silver photocatalyst of the present invention, under visible light illumination, the reactant liquor including strongly active copper cerium compound silver halide/silver photocatalyst passes through strong oxidizing property hydroxyl radical free radical OH, superoxide radical O with mercury fume2 -, hole h+Or Cl2/Br2/I2With the Hg in raw flue gas0There is a series of oxidation reaction, the Hg in elimination flue gas0, owing to the strongly active copper cerium compound silver halide/silver photocatalyst activity adopted is strong so that the activity of strong oxidizing property hydroxyl radical free radical OH is higher, therefore the demercuration effect of the flue gas hydrargyrum-removing method of employing copper cerium compound silver halide/silver photocatalyst of the present invention is better；It is additionally, since copper cerium compound silver halide/silver photocatalyst cost to reduce, therefore the cost of the flue gas hydrargyrum-removing method of employing copper cerium compound silver halide/silver photocatalyst of the present invention also decreases。
Accompanying drawing explanation
Fig. 1 is the overall procedure schematic diagram of copper cerium compound silver halide/silver photocatalyst preparation method of the present invention。
Fig. 2 is the schematic flow sheet of the flue gas hydrargyrum-removing method of employing copper cerium compound silver halide/silver photocatalyst of the present invention。
Fig. 3 is that employing copper cerium compound silver halide/silver photocatalyst of the present invention carries out the smoke demercuration device of use during flue gas demercuration。
Fig. 4 is that employing copper cerium compound silver halide/silver photocatalyst of the present invention carries out the demercuration design sketch that flue gas demercuration obtains。
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly, the present invention is described in further detail below in conjunction with the accompanying drawings and the specific embodiments。
Fig. 1 is the overall procedure schematic diagram of copper cerium compound silver halide/silver photocatalyst preparation method of the present invention。As it is shown in figure 1, copper cerium compound silver halide/silver photocatalyst preparation method of the present invention, comprise the steps:
Step 1, respectively by the cerous nitrate Ce (NO of certain mole3)3, copper nitrate Cu (NO3)2Stirring after being dissolved in deionized water, correspondence obtains Ce (NO3)3Solution, Cu (NO3)2Solution。
Step 2, under magnetic agitation mode, by Ce (NO3)3Solution adds Cu (NO3)2After in solution, continuing magnetic force stirs 20 minutes, obtains the first mixed solution；Afterwards, the first mixed solution adds the citric acid of certain mole, and successively magnetic agitation 30 minutes, stand 24 hours, obtain the second mixed solution；Wherein, add that the Citric Acid Dosage in the first mixed solution is copper nitrate and cerous nitrate mole sum 1～2 times。
Step 3, the second mixed solution is positioned in the water-bath of 70～80 DEG C and heats after 6～12 hours, be placed under sunlight and be exposed to the sun to dry state, this dry state sample is ground and is sized to more than 120 orders, obtains pressed powder CuyCe1-yOz；Wherein, y=0.05～0.3, z is that Ce and Cu forms the molal quantity of requisite oxygen during steady oxide。
Step 4, the silver nitrate of 0.1 mole is dissolved in a certain amount of deionized water after stir, obtain AgNO3Solution。
Step 5, by pressed powder CuyCe1-yOzAdd AgNO3In solution, also magnetic agitation, after 30 minutes, obtains solution A。
Step 6, by the Na of 0.1 mole2CO3After being dissolved in a certain amount of deionized water and stirring, obtain Na2CO3Solution。
Step 7, by Na2CO3Solution adds in solution A and magnetic agitation is after 20 minutes, adds potassium chloride (KCl), the potassium bromide KBr or potassium iodide KI of 0.1 mole, continues magnetic agitation 30 minutes, obtains B solution。
Step 8, B solution is placed in 50～80 DEG C of water bath heating devices under magnetic agitation mode and cultivates after 20 minutes, add the ethylene glycol of 10～25mL, continue to adopt magnetic means to stand 12～20 hours after stirring 20 minutes in condition of water bath heating, obtain C solution。
Step 9, employing deionized water are to, after C solution washing to neutrality, being placed in the baking oven of 60～80 DEG C dry 24 hours, and ground, be sized to more than 120 orders by dried object, obtain copper cerium compound silver halide/silver photocatalyst Ag/AgX/CuyCe1-yOz；Wherein, X is Cl, Br or I。
In copper cerium compound silver halide/silver photocatalyst preparation method of the present invention, the mol ratio of described Ag and described Ce is 5:1～10:1。
In a word, in copper cerium compound silver halide/silver photocatalyst preparation method of the present invention, the ceria CeO that will there is the strong absorbability in broadband but visible ray is hardly picked up2, copper oxide CuO and silver halide AgX compound, the transfer of semiconductor conduction band electronics and valence band hole can be promoted, strengthen efficiently separating of photo-generate electron-hole pair, strengthen the photocatalytic activity of obtained copper cerium compound silver halide/silver photocatalyst。It addition, ceria CeO2, copper oxide CuO be of many uses but cheap common materials, therefore obtained copper cerium compound silver halide/silver photocatalyst cost also decreases。
Fig. 2 is the schematic flow sheet of the flue gas hydrargyrum-removing method of employing copper cerium compound silver halide/silver photocatalyst of the present invention。As in figure 2 it is shown, a kind of flue gas hydrargyrum-removing method adopting copper cerium compound silver halide/silver photocatalyst of the present invention, comprise the steps:
Step J, by above-mentioned prepared copper cerium codope silver halide/silver photocatalyst Ag/AgX/CuyCe1-yOzIt is mixed and made into reactant liquor in the ratio of 1～5 g/l with water。
Step K, by the reactant liquor contacted with each other in radiation of visible light quartz glass class mercury removal device and mercury fume, strong oxidizing property hydroxyl radical free radical OH, the superoxide radical O of reactant liquor release2 -, hole h+Or Cl2/Br2/I2With the Hg in mercury fume0After there is oxidation reaction, the clean flue gas obtained is discharged into air。
In the flue gas hydrargyrum-removing method of employing copper cerium compound silver halide/silver photocatalyst of the present invention, it is seen that the reactant liquor that light irradiates, with flue gas, following course of reaction occurs:
Catalyst+h ν → e-+h+
e-+O2→·O2 -
h++H2O→·OH+H+
Hg0+h+/·OH/·O2 -→Hg2++…...
Hg0+Cl2/Br2/I2→HgCl2/HgBr2/HgI2
Here, hv represents the energy of visible ray。
In a word, in the flue gas hydrargyrum-removing method of employing copper cerium compound silver halide/silver photocatalyst of the present invention, under visible light illumination, the reactant liquor including strongly active copper cerium compound silver halide/silver photocatalyst passes through strong oxidizing property hydroxyl radical free radical OH, superoxide radical O with mercury fume2 -, hole h+Or Cl2/Br2/I2With the Hg in raw flue gas0There is a series of oxidation reaction, the Hg in elimination flue gas0, owing to the strongly active copper cerium compound silver halide/silver photocatalyst activity adopted is strong so that the activity of strong oxidizing property hydroxyl radical free radical OH is higher, therefore the demercuration effect of the flue gas hydrargyrum-removing method of employing copper cerium compound silver halide/silver photocatalyst of the present invention is better；It is additionally, since copper cerium compound silver halide/silver photocatalyst cost to reduce, therefore the cost of the flue gas hydrargyrum-removing method of employing copper cerium compound silver halide/silver photocatalyst of the present invention also decreases。
Embodiment
Fig. 3 is that employing copper cerium compound silver halide/silver photocatalyst of the present invention carries out the smoke demercuration device of use during flue gas demercuration。As shown in Figure 3, the present invention adopts the smoke demercuration device that copper cerium compound silver halide/silver photocatalyst uses when carrying out flue gas demercuration to include: for the steel cylinder 1 as raw flue gas source of the gas, Elemental Mercury osmos tube is installed to add the water bath with thermostatic control 3 of hydrargyrum to the raw flue gas source of the gas part from steel cylinder 1, for the blender 4 carrying out with mercury fume mixing by raw flue gas, for controlling steel cylinder 1 to water bath with thermostatic control 3, the effusion meter 2 of the gas flow of blender 4 corresponding output raw flue gas, the pending flue gas of blender 4 output enters the reactant liquor being loaded with bag copper-cerium-containing compound silver halide/silver photocatalyst under the control of effusion meter 2, reactant liquor is stirred and keeps the magnetic agitation water-bath 5 of constant temperature, temperature constant in magnetic agitation water-bath 5 is realized by thermocouple 7 and recirculated cooling water device 8 combined effect；Under the irradiation of the visible ray sent at visible light source 6, pending flue gas and reactant liquor occur demercuration to react in magnetic agitation water-bath 5。The demercuration flue gas of magnetic agitation water-bath 5 output enters the container 9 of the sodium hydroxide solution filling 20% mass fraction, and sodium hydroxide solution can absorb the sour gas of mixing in demercuration flue gas；And, sodium hydroxide absorbs container 9 and is provided with bypass, it is simple to detection nitric oxide NO and sulfur dioxide SO2Mass concentration；The demercuration flue gas removing sour gas is removed the steam carried in demercuration flue gas by sub-cooled groove 10；Afterwards, by the demercuration flue gas of the relatively dry cleaning obtained by being divided into three tunnels for cross valve 11, the first via is delivered to activated carbon adsorption bed 15 after Elemental Mercury tester 12 is tested, and test result is uploaded to the host computer 13 for recording, analyze hydrargyrum concentration by Elemental Mercury tester 12 simultaneously；Second tunnel is sent directly to activated carbon adsorption bed 15；3rd tunnel, after flue gas analyzer 14 carries out component analysis, enters activated carbon adsorption bed 15；After hydrargyrum in the demercuration flue gas comparing dried and clean, steam are adsorbed by activated carbon adsorption bed 15 further, by demercuration fume emission to atmospheric environment。Here, Elemental Mercury tester 12 adopts Germany's online mercury vapourmeter of VM3000。
In the present embodiment, raw flue gas is by N2、O2、CO2、SO2Form with NO；Wherein, N2、O2And CO2For basic smoke components, O2And CO2Volume content respectively 8% and 12%, N2For balanced gas。Raw flue gas total flow is 1.5 liters/min, by the N of Elemental Mercury osmos tube2Flow is 0.2 liter/min, Hg0、SO2With the mass concentration of NO respectively 50 micro-grams m3, 200 milli grams m3With 100 milli grams m3。In magnetic agitation water-bath 5, the internal diameter of reaction vessel is 10 centimetres, reaction vessel built-in power be 11 watts fluorescent lamp, electric filament lamp or LED class visible light source, and this visible light source is placed in conveniently carrying out in water-cooled quartz glass sleeve but。In reaction vessel, reactant liquor volume is about 1 liter, and reactant liquor height is about 15 centimetres, and the demercuration response time is set to 60 minutes。It addition, reactor bottom is additionally provided with gas distribution pipe, so that raw flue gas is full of whole reaction vessel equably。
Above-mentioned smoke demercuration device is prior art, repeats no more herein。
Adopt above-mentioned demercuration equipment, according to above-mentioned experiment parameter, adopt and described carry out the instantiation of demercuration as follows based on copper cerium compound silver halide/silver photocatalyst demercuration method。
Example one
Ce(NO3)3The cerous nitrate that solution is 0.02 mole is dissolved in 100 ml deionized water, Cu (NO3)2The copper nitrate that solution is 0.0023 mole is dissolved in 50 ml deionized water, and Citric Acid Dosage is 2 times of copper nitrate and cerous nitrate mole sum, and gained pressed powder is Cu0.1Ce0.9Oz, photocatalyst be Ag/AgCl/Cu0.1Ce0.9OzOr Ag/AgBr/Cu0.1Ce0.9Oz。Employing photocatalyst is Ag/AgCl/Cu0.1Ce0.9OzThe experiment parameter carrying out flue gas demercuration is as shown in table 1:
The first flue gas demercuration experiment parameter of table 1
| Reaction temperature/pressure | Catalyst amount | Hg0Concentration | Smoke components |
| 25 DEG C/normal pressure | 2 g/l | 50 micro-grams m3 | N2、O2、CO2 |
Flue gas demercuration experiment parameter according to table 1, adopts photocatalyst Ag/AgCl/Cu0.1Ce0.9OzCarry out simple substance Hg0The removal efficiency of elimination is about 93%。
Example two
Adopt the photocatalyst Ag/AgBr/Cu of example one preparation0.1Ce0.9Oz, flue gas demercuration experiment parameter as shown in table 2 is set:
Table 2 the second flue gas demercuration experiment parameter
| Reaction temperature/pressure | Catalyst amount | Hg0Concentration | Smoke components |
| 40 DEG C/normal pressure | 2 g/l | 50 micro-grams m3 | N2、O2、CO2 |
Flue gas demercuration experiment parameter according to table 2, adopts photocatalyst Ag/AgBr/Cu0.1Ce0.9OzCarry out simple substance Hg0The removal efficiency of elimination is about 90%。
Example three
Ce(NO3)3The cerous nitrate that solution is 0.02 mole is dissolved in 100 ml deionized water, Cu (NO3)2The copper nitrate that solution is 0.0086 mole is dissolved in 75 ml deionized water, and Citric Acid Dosage is 1.5 times of copper nitrate and cerous nitrate mole sum, and gained pressed powder is Cu0.3Ce0.7Oz, photocatalyst be Ag/AgBr/Cu0.3Ce0.7OzOr Ag/AgI/Cu0.3Ce0.7Oz。
Employing photocatalyst is Ag/AgBr/Cu0.3Ce0.7OzThe experiment parameter carrying out flue gas demercuration is as shown in table 3:
The third flue gas demercuration experiment parameter of table 3
| Reaction temperature/pressure | Catalyst amount | Hg0Concentration | Smoke components |
| 25 DEG C/normal pressure | 3 g/l | 50 micro-grams m3 | N2、O2、CO2、NO |
Flue gas demercuration experiment parameter according to table 3, adopts photocatalyst Ag/AgBr/Cu0.3Ce0.7OzCarry out simple substance Hg0The removal efficiency of elimination is about 88%。
Example four
Adopt and the photocatalyst Ag/AgI/Cu of example three preparation0.3Ce0.7Oz, flue gas demercuration experiment parameter as shown in table 4 is set:
The 4th kind of flue gas demercuration experiment parameter of table 4
| Reaction temperature/pressure | Catalyst amount | Hg0Concentration | Smoke components |
| 30 DEG C/normal pressure | 2 g/l | 50 micro-grams m3 | N2、O2、CO2、SO2、NO |
Flue gas demercuration experiment parameter according to table 4, adopts photocatalyst Ag/AgI/Cu0.3Ce0.7OzCarry out simple substance Hg0The removal efficiency of elimination is about 85%。
Fig. 4 is that employing copper cerium compound silver halide/silver photocatalyst of the present invention carries out the demercuration design sketch that flue gas demercuration obtains。As shown in Figure 4, by above-mentioned experiment it can be seen that the factors such as reaction temperature, smoke components, catalyst amount are to Elemental Mercury Hg0Removal efficiency all have impact。In practical application, suitable flue gas demercuration parameter can be selected as required。
In sum, these are only presently preferred embodiments of the present invention, be not intended to limit protection scope of the present invention。All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention。
Claims (3)
1. copper cerium compound silver halide/silver photocatalyst preparation method, it is characterised in that described catalyst manufacture method comprises the steps:
Step 1, respectively by the cerous nitrate Ce (NO of certain mole3)3, copper nitrate Cu (NO3)2Stirring after being dissolved in deionized water, correspondence obtains Ce (NO3)3Solution, Cu (NO3)2Solution；
Step 2, under magnetic agitation mode, by Ce (NO3)3Solution adds Cu (NO3)2After in solution, continuing magnetic force stirs 20 minutes, obtains the first mixed solution；Afterwards, in the first mixed solution add citric acid, and successively magnetic agitation 30 minutes, stand 24 hours, obtain the second mixed solution；Wherein, add that the Citric Acid Dosage in the first mixed solution is copper nitrate and cerous nitrate mole sum 1～2 times；
Step 3, the second mixed solution is positioned in the water-bath of 70～80 DEG C and heats after 6～12 hours, be placed under sunlight and be exposed to the sun to dry state, this dry state sample is ground and is sized to more than 120 orders, obtains pressed powder CuyCe1-yOz；Wherein, y=0.05～0.3, z is that Ce and Cu forms the molal quantity of requisite oxygen during steady oxide；
Step 4, the silver nitrate of 0.1 mole is dissolved in a certain amount of deionized water after stir, obtain AgNO3Solution；
Step 5, by pressed powder CuyCe1-yOzAdd AgNO3In solution, also magnetic agitation, after 30 minutes, obtains solution A；
Step 6, by the Na of 0.1 mole2CO3After being dissolved in a certain amount of deionized water and stirring, obtain Na2CO3Solution；
Step 7, by Na2CO3Solution adds in solution A and magnetic agitation is after 20 minutes, adds potassium chloride (KCl), the potassium bromide KBr or potassium iodide KI of 0.1 mole, continues magnetic agitation 30 minutes, obtains B solution；
Step 8, B solution is placed in 50～80 DEG C of water bath heating devices under magnetic agitation mode and cultivates after 20 minutes, add the ethylene glycol of 10～25mL, continue to adopt magnetic means to stand 12～20 hours after stirring 20 minutes in condition of water bath heating, obtain C solution；
Step 9, employing deionized water are to, after C solution washing to neutrality, being placed in the baking oven of 60～80 DEG C dry 24 hours, and ground, be sized to more than 120 orders by dried object, obtain copper cerium compound silver halide/silver photocatalyst Ag/AgX/CuyCe1-yOz；Wherein, X is Cl, Br or I。
2. copper cerium compound silver halide/silver photocatalyst preparation method according to claim 1, it is characterised in that the mol ratio of described Ag and described Ce is 5:1～10:1。
3. the flue gas hydrargyrum-removing method adopting copper cerium compound silver halide/silver photocatalyst, it is characterised in that described flue gas hydrargyrum-removing method comprises the steps:
Step J, the copper cerium codope silver halide/silver photocatalyst Ag/AgX/Cu that will prepare in claim 1 or 2yCe1-yOzIt is mixed and made into reactant liquor in the ratio of 1～5 g/l with water；
Step K, by the reactant liquor contacted with each other in radiation of visible light quartz glass class mercury removal device and mercury fume, strong oxidizing property hydroxyl radical free radical OH, the superoxide radical O of reactant liquor release2 -, hole h+Or Cl2/Br2/I2With the Hg in mercury fume0After there is oxidation reaction, the clean flue gas obtained is discharged into air。
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