CN110339710B - Microwave coupling ultraviolet light catalytic oxidation Hg0Purification system and method - Google Patents
Microwave coupling ultraviolet light catalytic oxidation Hg0Purification system and method Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 55
- 230000003647 oxidation Effects 0.000 title claims abstract description 48
- 230000008878 coupling Effects 0.000 title claims abstract description 27
- 238000010168 coupling process Methods 0.000 title claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 51
- 230000001590 oxidative effect Effects 0.000 claims abstract description 40
- 238000010521 absorption reaction Methods 0.000 claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 24
- 239000003546 flue gas Substances 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000012159 carrier gas Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims description 34
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 235000011164 potassium chloride Nutrition 0.000 claims description 16
- 239000001103 potassium chloride Substances 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 9
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 9
- 229960002218 sodium chlorite Drugs 0.000 claims description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229960002523 mercuric chloride Drugs 0.000 claims description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 238000005202 decontamination Methods 0.000 abstract description 2
- 230000003588 decontaminative effect Effects 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 24
- 239000002131 composite material Substances 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- 230000002745 absorbent Effects 0.000 description 9
- 239000002250 absorbent Substances 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012717 electrostatic precipitator Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 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
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/108—Halogens or halogen compounds
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
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Abstract
The invention discloses a microwave coupling ultraviolet light catalytic oxidation Hg, belonging to the technical field of flue gas purification0A decontamination system and method. The microwave coupling ultraviolet light catalyzes and oxidizes Hg0The purification system comprises a microwave generator, an electrodeless lamp, a photocatalytic reactor and a subsequent absorption device, wherein firstly, nitrogen carrier gas enters a mercury generator, a water bath kettle vaporizes solid mercury, and Hg is evaporated0The vapor enters a microwave reactor, microwaves are used for heating and exciting an electrodeless lamp, a liquid oxidant is catalyzed and activated in a photocatalytic reactor, and the generated high-activity free radicals are used for treating Hg0Oxidation is carried out. The generated oxidized mercury enters a subsequent absorption system to be absorbed, and finally the gas after the demercuration treatment is discharged. The invention realizes the purpose of burning Hg in the coal-fired flue gas0The high-efficiency oxidation is the high integration and promotion of the prior demercuration oxidation equipment, and can solve the problem of Hg in the prior flue gas pollutants0Difficult to be removed by oxidation, large occupied area and high operation cost.
Description
Technical Field
The invention belongs to the technical field of flue gas purification, and particularly relates to microwave coupling ultraviolet light catalytic oxidation of Hg0A decontamination system and method.
Background
Artificial emission of mercury into the atmosphere has become an important environmental problem, and attention is paid to various countries because methyl mercury generated by conversion of artificially emitted mercury has great toxicity, durability and bioaccumulation. At present, the main power source in China is provided by a coal-fired power plant, but the flue gas generated by the coal-fired power plant contains a large amount of harmful substances such as SO2、NO、Hg0And the like, therefore, the China government promulgates the 'emission standard of atmospheric pollutants for thermal power plants' (GB 13223-x、SO2And Hg0And (4) discharging. Among them, mercury as a heavy metal is difficult to degrade by continuous accumulation in trace amount and causes considerable toxicity to human body, so it is necessary to find an efficient mercury treatment method.
The mercury is mainly from flue gas emission of coal-fired power plant, municipal refuse incinerator and medical wasteAn incinerator for burning garbage. Among them, mercury in flue gas of coal-fired power plants is one of the main sources of mercury pollution, and the emission of mercury into nature can become mercuride harmful to organisms through a series of biological processes. The mercury has the characteristics of strong toxicity, high volatility, durability, bioaccumulation and the like. Mercurides generally fall into 3 forms: elemental mercury (Hg)0) Mercury oxide (Hg)2+) Particulate mercury (Hg)p). Oxidized mercury and particulate mercury can be removed by subsequent flue gas treatment in power plants, such as using typical Air Pollution Control Devices (APCD), electrostatic precipitators (ESP), wet FGD (flue gas desulfurization), etc., elemental mercury is practically insoluble in water and difficult to adsorb by other substances, and thus elemental mercury is a major problem for mercury treatment. Under the existing conditions, Hg is oxidized by an oxidation method0Oxidation to Hg2+Then using Hg2+Is to treat Hg0An effective method of (1). The SCR process can generate a certain oxidation effect on mercury, but because the SCR process is mainly a denitration process and has the defects of high investment cost, wide occupied area and the like, the search for a new mercury removal technology is a strategic need for realizing sustainable development in China.
In order to solve the problems of high cost, large occupied area and the like of the existing demercuration process, the invention aims to efficiently oxidize Hg in a microwave coupling ultraviolet mode0To change it into Hg2+Thereby achieving the removal of Hg0The effect of (1). In recent years, microwaves have been widely applied to water treatment processes, and the combined action of the thermal effect and the non-thermal effect of the microwaves has a great positive effect on the removal of pollutants. Ultraviolet light irradiation also has a large positive effect on the generation of free radicals, which are also constantly proven to be efficient oxidants for oxidizing contaminants. The invention aims to realize Hg alignment by using a microwave-ultraviolet light coupling mode0The purpose of efficient oxidation and removal is achieved.
Disclosure of Invention
The invention aims to provide a microwave coupling ultraviolet light catalytic oxidation method for Hg0The purification system and the method are characterized in that the microwave coupling ultraviolet light is used for catalyzing and oxidizing Hg0The purification system comprises a microwave generator, an electrodeless lamp, a photocatalytic reactor and a subsequent absorption device, wherein nitrogen gasThe carrier gas system 1, the mass flowmeter 2 and the mercury generator 3 are connected in series, and the mercury generator 3 is respectively connected with the microwave reactor 7 and the connection node of the drying device 9 and the continuous absorption system 8 through three regulating valves; the subsequent absorption system 8 is connected with the microwave reactor 7; the drying device 9 is connected with the mercury detector 10 and the flue gas analyzer 4 in series; the photocatalytic reactor 6 and the electrodeless lamp 5 are installed in the microwave reactor 7.
Microwave coupling ultraviolet light catalytic oxidation Hg0Hg of purification system0A purification method, characterized by comprising the steps of:
(1) the microwave generator is used for generating microwaves, the heat effect generated by the microwaves is used for rapidly heating the photocatalytic reactor, the oxidation effect of the liquid-phase oxidant is improved within a certain range through heating, meanwhile, the microwaves also have a non-heat effect, the non-heat effect of microwave radiation has a remarkable influence on the property of the surface of the catalyst consisting of oxidant molecules and water molecules, and the further oxidation of an intermediate Hg0 is facilitated;
(2) exciting the electrodeless lamp by microwave to generate ultraviolet light; ultraviolet light irradiates the liquid phase oxidant to generate high-activity free radicals which are used for efficiently oxidizing Hg0Convert it into Hg2+(ii) a Simultaneously ultraviolet light to convert O2Excited as ozone O3；O3Has strong oxidizing property and can further promote Hg0To Hg2+The oxidation effect is improved;
(3) the photocatalytic reactor is used for containing a liquid-phase oxidant and an electrodeless lamp for catalytic oxidation, the front section of the photocatalytic reactor is connected with a mercury generating device for generating Hg0Nitrogen is taken as carrier gas to be subjected to catalytic oxidation in a photocatalytic reaction, a microwave coupling ultraviolet lamp is used for acting on a liquid-phase oxidant to generate free radicals such as OH, Cl and the like, and the strong oxidizing property of the free radicals is utilized to treat Hg0Oxidation is carried out.
(4) Introducing the oxidized nitrogen into a subsequent absorption system, and absorbing with potassium chloride and sodium chloride solution in the absorption system, wherein Cl in the solution-Ions will react with Hg2+Ion combination to form stable mercuric chloride HgCl solution to remove Hg0The purpose of (1).
The liquid-phase oxidant consists of one or more of hydrogen peroxide, sodium persulfate, sodium chlorite and sodium hypochlorite,
the liquid-phase oxidizing agent mainly comprises one or more of hydrogen peroxide, sodium persulfate, sodium chlorite and sodium hypochlorite, wherein the concentration of the hydrogen peroxide is 10-20 wt%, the concentration of the sodium persulfate is 5-10%, the concentration of the sodium chlorite is 0.05-0.1 wt%, and the pH range is 4.5-6.5.
The absorption liquid consists of potassium chloride and sodium chloride solutions, wherein the concentration of potassium chloride is 5 wt%, the concentration of sodium chloride is 6 wt%, and the pH range is 7.
The microwave coupling ultraviolet lamp plays a role in promoting the microwave coupling ultraviolet lamp to catalytically oxidize Hg in the liquid-phase oxidant0The operating conditions were as follows:
(1) the gas speed of nitrogen carrier gas is 150L/h;
(2) the temperature of the nitrogen before entering the mercury generator is 20-25 ℃, and the water bath temperature of the mercury generator is 60 ℃;
(3) the temperature of the microwave reactor is 40-90 ℃;
(4) the power of the microwave-excited electrodeless lamp is 300-;
(5) the adding amount of the liquid-phase oxidant is 500 ml;
(6) the temperature range of the absorption liquid inlet smoke is 20-25 ℃, and the temperature of the absorption liquid is 20-30 ℃.
The invention has the beneficial effects that:
1. the method realizes the Hg in the coal-fired flue gas through microwave coupling ultraviolet light catalytic oxidation0The high-efficiency oxidation is the high integration and promotion of the prior demercuration oxidation equipment, and can solve the problem of Hg in the prior flue gas pollutants0Difficult to be removed by oxidation, large occupied area and high operation cost.
2. The invention realizes the rapid and efficient heating of the oxidant through the microwave reactor, and the heat effect and the non-heat effect of the oxidant are corresponding to Hg0The oxidation reaction also produces a positive effect. Meanwhile, the utilization rate of the ultraviolet light is improved by the mode of exciting the electrodeless lamp by the microwave to generate the ultraviolet light, the operation and the simultaneous regulation and control are more convenient,on the one hand, the utilization rate of the oxidant is improved, and on the other hand, Hg is promoted0To Hg2+The oxidation process of (2) and simultaneously, the operation cost is reduced, and the oxidation efficiency of the oxide is improved.
3. The high-activity free radicals generated by the photocatalytic reaction system are green and efficient active species, so that on one hand, the oxidation rate of pollutants is greatly accelerated, and the derivatives and reaction products of the free radicals are nontoxic and harmless and cannot generate corrosion on the reaction system;
4. the invention effectively utilizes the microwave to heat and excite the electrodeless lamp to generate ultraviolet light, thereby reducing extra energy output and lowering cost on one hand, being beneficial to realizing synchronous temperature rise and light adding on the other hand, and promoting the high-efficiency operation of oxidation reaction.
5. The microwave coupling ultraviolet light catalytic oxidation technology is suitable for the mercury treatment of various coal-fired power plants and other mercury-producing plants, and solves the problem of Hg0One of the possibilities for contamination.
Drawings
Fig. 1 is a schematic diagram of a microwave coupling ultraviolet photocatalytic oxidation Hg0 system.
In the figure: 1-nitrogen carrier gas system; 2-mass flow meter; 3-a mercury generator; 4-a flue gas analyzer; 5-electrodeless lamp; 6-a photocatalytic reactor; 7-a microwave reactor; 8-a subsequent absorption system;
Detailed Description
The invention provides a microwave coupling ultraviolet light catalytic oxidation Hg0The invention is described below with reference to the drawings and examples.
Fig. 1 is a schematic diagram of a system for microwave coupling ultraviolet photocatalytic oxidation of Hg 0. The microwave coupling ultraviolet light catalytic oxidation Hg shown in the figure0The purification system comprises a microwave generator, an electrodeless lamp, a photocatalytic reactor and a subsequent absorption device, wherein a nitrogen carrier gas system 1, a mass flow meter 2 and a mercury generator 3 are connected in series, and the mercury generator 3 is respectively connected with each connecting node of the microwave reactor 7 and a drying device 9 and the subsequent absorption system 8 through three regulating valves; a subsequent absorption system 8 and a microwave reactor 7; drying device 9, mercury detector 10 and cigaretteThe gas analyzers 4 are connected in series; the photocatalytic reactor 6 and the electrodeless lamp 5 are installed in the microwave reactor 7. The present invention will be further illustrated by the following examples.
Hg of the system0The purification principle is as follows:
firstly, nitrogen carrier gas enters a mercury generator, solid mercury is vaporized by a water bath kettle, and Hg is generated0The steam enters a microwave reactor, and microwaves are used for heating and exciting an electrodeless lamp. Subsequently, the liquid composite oxidant is catalytically activated in the photocatalytic reactor to generate a plurality of high-activity free radicals. Then, high active free radical is to Hg0Oxidation is carried out. The generated oxidized mercury enters a subsequent absorption system to be absorbed. Finally, the gas after the demercuration treatment is discharged. The reaction mechanism of the steps of the invention is as follows:
the liquid phase oxidant reaction mechanism is as follows:
S2O8 2-+H+→HS2O8 -
HS2O8 -→SO4+HSO4 -
SO4→SO3+(1/2)O2
SO3+H2O→H2SO4
the ultraviolet light catalytic oxidation reaction mechanism is as follows:
H2O2+hv→2HO·
HO·+Cl-→ClOH·-
ClOH·-+H+→Cl·+H2O
Cl·+Cl·→Cl2
2H++ClO-+Cl-→Cl2+2H2O
S2O8 2-+H2O→HSO4 -+SO4·-+OH·
S2O8 2-+hv+heat→2SO4·-
H2O+SO4·-→H++SO4 2-+HO·
HO·+SO4·-→HSO5
-2OH·→H2O2
the mercury removal reaction mechanism is as follows:
4H2O+5Hg+2ClO2→5Hg2++2Cl-+8OH-
2SO2+ClO2→2SO3+Cl-
Cl·+Cl·→Cl2+Hg→Hg2++2Cl-
2OH·+Hg+2H+→Hg2++2H2O
Hg+O3→HgO+O2，Hg+O→HgO，Hg+HO2→HgO+OH
the reaction mechanism of KCl, NaCl and other absorption liquids is as follows:
Hg2++Cl-→HgCl
by adopting the microwave coupling ultraviolet light catalytic demercuration treatment of the invention, the treatment effect is shown in table 1:
TABLE 1 Demercurization Effect
| Item | Before treatment | After treatment | Efficiency of removal |
| Hg0Concentration of | 30μg/m3 | 3-1.5μg/m3 | 90-95％ |
The microwave coupling ultraviolet light catalytic demercuration treatment method can meet the current atmospheric pollutant emission standard of the thermal power plant under the typical operating condition conditions of the thermal power plant in China. Compared with a common oxidation absorption system, the treatment system has the advantages of lower capital construction and operation cost, simpler operation and more obvious removal effect. The invention is suitable for various boilers and can realize efficient and synergistic removal of various flue gas pollutants, so the invention has good environmental benefit and economic benefit and wide application prospect.
Example 1
Liquid-phase composite oxidant: the sodium persulfate concentration was 5% wt, pH 5.5.
Liquid phase absorbent: the potassium chloride concentration was 5% wt, pH 7.
The reaction conditions of the microwave-coupled ultraviolet catalytic oxidation desulfurization and denitrification system are shown in table 2.
TABLE 2 reaction conditions
| Condition | Range |
| Microwave set temperature | 50℃ |
| Microwave setting power | 300W |
| Water bath temperature of mercury generator | 60℃ |
| Energy density of photocatalyst reaction device | 300KW/m3 |
| Temperature of absorption liquid | 20℃ |
Purifying the flue gas according to the conditions, and detecting to obtain: the demercuration efficiency reaches 92 percent.
Example 2
Liquid-phase composite oxidant: the sodium persulfate concentration was 10% wt, pH 5.
Liquid phase absorbent: the potassium chloride concentration was 5% wt, pH 7.
The reaction conditions of the microwave-coupled ultraviolet catalytic oxidation desulfurization and denitrification system are shown in table 3.
TABLE 3 reaction conditions
| Condition | Range |
| Microwave set temperature | 50℃ |
| Microwave setting power | 300W |
| Water bath temperature of mercury generator | 60℃ |
| Energy density of photocatalyst reaction device | 300KW/m3 |
| Temperature of absorption liquid | 20℃ |
Purifying the flue gas according to the conditions, and detecting to obtain: the demercuration efficiency reaches 94 percent.
Example 3
Liquid-phase composite oxidant: the hydrogen peroxide concentration was 10% wt, pH 6.
Liquid phase absorbent: the potassium chloride concentration was 5% wt, pH 7.
The reaction conditions of the microwave-coupled ultraviolet catalytic oxidation desulfurization and denitrification system are shown in Table 4.
TABLE 4 reaction conditions
| Condition | Range |
| Microwave set temperature | 50℃ |
| Microwave setting power | 300W |
| Water bath temperature of mercury generator | 60℃ |
| Energy density of photocatalyst reaction device | 300KW/m3 |
| Temperature of absorption liquid | 20℃ |
Purifying the flue gas according to the conditions, and detecting to obtain: the demercuration efficiency reaches 93 percent.
Example 4
Liquid-phase composite oxidant: the hydrogen peroxide concentration was 20% wt, pH 5.6.
Liquid phase absorbent: the potassium chloride concentration was 5% wt, pH 7.
The reaction conditions of the microwave-coupled ultraviolet catalytic oxidation desulfurization and denitrification system are shown in Table 5.
TABLE 5 reaction conditions
| Condition | Range |
| Microwave set temperature | 50℃ |
| Microwave setting power | 300W |
| Water bath temperature of mercury generator | 60℃ |
| Energy density of photocatalyst reaction device | 300KW/m3 |
| Temperature of absorption liquid | 20℃ |
Purifying the flue gas according to the conditions, and detecting to obtain: the demercuration efficiency reaches 90 percent.
Example 5
Liquid-phase composite oxidant: the sodium chlorite concentration was 0.1% wt, pH 5.5.
Liquid phase absorbent: the potassium chloride concentration was 5% wt, pH 7.
The reaction conditions of the microwave-coupled ultraviolet catalytic oxidation desulfurization and denitrification system are shown in Table 6.
TABLE 6 reaction conditions
| Condition | Range |
| Microwave set temperature | 50℃ |
| Microwave setting power | 300W |
| Water bath temperature of mercury generator | 60℃ |
| Energy density of photocatalyst reaction device | 300KW/m3 |
| Temperature of absorption liquid | 20℃ |
Purifying the flue gas according to the conditions, and detecting to obtain: the demercuration efficiency reaches 92 percent.
Example 6
Liquid-phase composite oxidant: the sodium chlorite concentration was 0.05% wt, pH 6.
Liquid phase absorbent: the potassium chloride concentration was 5% wt, pH 7.
The reaction conditions of the microwave-coupled ultraviolet photocatalytic oxidation desulfurization and denitrification system are shown in Table 7.
TABLE 7 reaction conditions
| Condition | Range |
| Microwave set temperature | 50℃ |
| Microwave setting power | 300W |
| Water bath temperature of mercury generator | 60℃ |
| Energy density of photocatalyst reaction device | 300KW/m3 |
| Temperature of absorption liquid | 20℃ |
Purifying the flue gas according to the conditions, and detecting to obtain: the demercuration efficiency reaches 94 percent.
Example 7
Liquid-phase composite oxidant: the concentration ratio of sodium chlorite to sodium persulfate was 0.05: 10% wt, and the pH was 5.5.
Liquid phase absorbent: the potassium chloride concentration was 5% wt, pH 7.
The reaction conditions of the microwave-coupled ultraviolet photocatalytic oxidation desulfurization and denitrification system are shown in Table 8.
TABLE 8 reaction conditions
| Condition | Range |
| Microwave set temperature | 50℃ |
| Microwave setting power | 300W |
| Water bath temperature of mercury generator | 60℃ |
| Energy density of photocatalyst reaction device | 300KW/m3 |
| Temperature of absorption liquid | 20℃ |
Purifying the flue gas according to the conditions, and detecting to obtain: the demercuration efficiency reaches 94 percent.
Example 8
Liquid-phase composite oxidant: the ratio of the concentration of hydrogen peroxide to sodium persulfate was 10: 10% wt, and the pH was 5.
Liquid phase absorbent: the potassium chloride concentration was 5% wt, pH 7.
The reaction conditions of the microwave-coupled ultraviolet catalytic oxidation desulfurization and denitrification system are shown in Table 9.
TABLE 9 reaction conditions
| Condition | Range |
| Microwave set temperature | 50℃ |
| Microwave setting power | 300W |
| Water bath temperature of mercury generator | 60℃ |
| Energy density of photocatalyst reaction device | 300KW/m3 |
| Temperature of absorption liquid | 20℃ |
Purifying the flue gas according to the conditions, and detecting to obtain: the demercuration efficiency reaches 93 percent.
Example 9
Liquid-phase composite oxidant: the ratio of sodium chlorite to hydrogen peroxide concentration was 0.05: 10% wt, pH 5.5.
Liquid phase absorbent: the potassium chloride concentration was 5% wt, pH 7.
The reaction conditions of the microwave-coupled ultraviolet photocatalytic oxidation desulfurization and denitrification system are shown in Table 10.
TABLE 10 reaction conditions
| Condition | Range |
| Microwave set temperature | 50℃ |
| Microwave setting power | 300W |
| Water bath temperature of mercury generator | 60℃ |
| Energy density of photocatalyst reaction device | 300KW/m3 |
| Temperature of absorption liquid | 20℃ |
Purifying the flue gas according to the conditions, and detecting to obtain: the demercuration efficiency reaches 94 percent.
Claims (3)
1. Microwave coupling ultraviolet light catalytic oxidation Hg0The purification system is characterized in that the microwave coupling ultraviolet light is used for catalyzing and oxidizing Hg0The purification system comprises a microwave generator, an electrodeless lamp, a photocatalytic reactor and a subsequent absorption device, wherein a nitrogen carrier gas system (1), a mass flow meter (2) and a mercury generator (3) are connected in series, and one output of the mercury generator (3) is connected in series with the microwave reactor (7), the subsequent absorption system (8), a drying device (9), a mercury detector (10) and a flue gas analyzer (4) through a No. 1 regulating valve; the other path of output of the mercury generator (3) is formed by connecting a 2# regulating valve and a 3# regulating valve in series; the other path of output of the mercury generator (3) is connected in parallel with a circuit formed by connecting a 1# regulating valve, a microwave reactor (7) and a subsequent absorption system (8) in series; the photocatalytic reactor (6) and the electrodeless lamp (5) are arranged in the microwave reactor (7).
2. Microwave coupling ultraviolet light catalytic oxidation Hg0Hg of purification system0A purification method, characterized by comprising the steps of:
(1) the microwave generator is used for generating microwaves, the heat effect generated by the microwaves is used for rapidly heating the photocatalytic reactor, the oxidation effect of the liquid-phase oxidant is improved within a certain range through heating, meanwhile, the microwaves also have a non-heat effect, the non-heat effect of microwave radiation has a remarkable influence on the property of the surface of the catalyst consisting of oxidant molecules and water molecules, and the further oxidation of an intermediate Hg0 is facilitated;
(2) exciting the electrodeless lamp by microwave to generate ultraviolet light; ultraviolet light irradiates the liquid phase oxidant to generate high-activity free radicals which are used for efficiently oxidizing Hg0Convert it into Hg2+(ii) a Simultaneously ultraviolet light to convert O2Excited as ozone O3；O3Has strong oxidizing property and can further promote Hg0To Hg2+The oxidation effect is improved;
(3) the photocatalytic reactor is used for containing a liquid-phase oxidant and an electrodeless lamp for catalytic oxidation, the front section of the photocatalytic reactor is connected with a mercury generating device for generating Hg0Nitrogen is taken as carrier gas to be subjected to catalytic oxidation in a photocatalytic reaction, liquid-phase oxidant is acted by a microwave coupling ultraviolet lamp, OH and Cl free radicals can be generated, and the strong oxidizing property of the free radicals is utilized to react Hg0Carrying out oxidation; the liquid-phase oxidant consists of one or more of hydrogen peroxide, sodium persulfate, sodium chlorite and sodium hypochlorite, wherein the concentration of the hydrogen peroxide is 10-20 wt%, the concentration of the sodium persulfate is 5-10%, the concentration of the sodium chlorite is 0.05-0.1 wt%, and the pH range is 4.5-6.5;
(4) introducing the oxidized nitrogen into a subsequent absorption system, and absorbing with potassium chloride and sodium chloride solution in the absorption system, wherein Cl in the solution-Ions will react with Hg2+Ion combination to form stable mercuric chloride HgCl solution to remove Hg0The object of (a); the absorption liquid consists of potassium chloride and sodium chloride solutions, wherein the concentration of potassium chloride is 5 wt%, the concentration of sodium chloride is 6 wt%, and the pH range is 7.
3. The microwave-coupled ultraviolet photocatalytic oxidation of Hg according to claim 20Hg of purification system0The purification method is characterized in that the microwave coupling ultraviolet lamp acts on the liquid-phase oxidant to promote the microwave coupling ultraviolet lamp to catalytically oxidize Hg0The operating conditions were as follows:
(1) the gas speed of nitrogen carrier gas is 150L/h;
(2) the temperature of the nitrogen before entering the mercury generator is 20-25 ℃, and the water bath temperature of the mercury generator is 60 ℃;
(3) the temperature of the microwave reactor is 40-90 ℃;
(4) the power of the microwave-excited electrodeless lamp is 300-;
(5) the adding amount of the liquid-phase oxidant is 500 ml;
(6) the temperature range of the absorption liquid inlet smoke is 20-25 ℃, and the temperature of the absorption liquid is 20-30 ℃.
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