CN105536466B - The device and method of multi-pollutant in a kind of photocatalytic oxidation removing flue gas - Google Patents

The device and method of multi-pollutant in a kind of photocatalytic oxidation removing flue gas Download PDF

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CN105536466B
CN105536466B CN201610049882.XA CN201610049882A CN105536466B CN 105536466 B CN105536466 B CN 105536466B CN 201610049882 A CN201610049882 A CN 201610049882A CN 105536466 B CN105536466 B CN 105536466B
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flue gas
pollutant
catalysis
composite oxidant
priming reaction
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CN105536466A (en
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郝润龙
赵毅
袁博
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North China Electric Power University
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North China Electric Power University
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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
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides
    • B01D2251/1065—Organic peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B01D2255/2027—Sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/70—Non-metallic catalysts, additives or dopants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/70—Non-metallic catalysts, additives or dopants
    • B01D2255/707—Additives or dopants
    • 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
    • B01D2259/00—Type of treatment
    • B01D2259/12—Methods and means for introducing reactants
    • B01D2259/124—Liquid reactants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/10—Nitrogen; Compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/10—Nitrogen; Compounds thereof
    • F23J2215/101—Nitrous oxide (N2O)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/20—Sulfur; Compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2219/00—Treatment devices
    • F23J2219/10—Catalytic reduction devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The present invention relates to the device and method of multi-pollutant in a kind of photocatalytic oxidation removing flue gas.Fume afterheat is utilized and mist generating device is arranged in the pipeline between air preheater and electrostatic precipitator, it uses the structure of big pipe sleeve tubule, big pipe conveying composite oxidant, intratubular compressed air makes composite oxidant formation fluidized state, heat smoke exchanges heat with composite oxidant simultaneously, composite oxidant is set to be atomized into fine droplets, it is atomized composite oxidant and enters light co-catalysis priming reaction device by catalytic activation, a variety of free radicals are produced to spray from the outlet of light co-catalysis priming reaction device, with the smoke contacts after dedusting, NO in flue gas is changed into the NOx of high-valence state, by Hg0It is oxidized to Hg2+, NOx, Hg2+And SO2Enter absorption plant by absorbing and removing with flue gas, realize efficient, the collaboration of desulfurization denitration demercuration, removing product is high-quality composite fertilizer, is conducive to recycling, with higher economy and environmental benefit.

Description

The device and method of multi-pollutant in a kind of photocatalytic oxidation removing flue gas
Technical field
The invention belongs to flue gases purification field, more particularly to a kind of photocatalytic oxidation removes multi-pollutant in flue gas Device and method.
Background technology
China's atmosphere pollution belongs to typical coal-smoke pollution, and wherein sulfur dioxide, nitrogen oxides and heavy metal is coal-fired The significant pollutant of flue gas, sulfur dioxide and nitrogen oxides are the main sources of acid rain, and nitrogen oxides is also to form photochemistry One of main predecessor of smog, and Elemental Mercury is the characteristics of have strong toxicity, form stable and difficult for biological degradation.In recent years, Because the discharge capacity of sulfur dioxide, nitrogen oxides and heavy metal in coal-fired flue-gas is significantly improved, China's haze is caused to take place frequently, seriously Compromise people's health and ecological environment.
The main flume desulfurization technology that coal-burning power plant of China is used is Wet Limestone-plastering (WFGD), the technique Have the advantages that technology maturation, desulfuration efficiency are wide compared with high, coal accommodation, it is big to handle exhaust gas volumn, but there is system complex, energy High deficiency is consumed, and 95% desulfuration efficiency can not meet especially area 50mg/m3Concentration of emission limit value.And tradition SCR The problem of there is cost high, short life in catalyst, and the escaping of ammonia, catalyst poisoning and waste catalyst is difficult etc. also turns into The bottleneck of SCR denitration technology development.Charcoal absorption demercuration method, which has high, the discarded activated carbon of cost and is difficult to recycle etc., asks Topic.Meanwhile, this classification processing mode has that floor space is big, system run all right is poor, equipment energy consumption is higher and secondary Therefore the problems such as pollution, therefore, research and develop the integrated removing sulfuldioxide of emerging coal-fired flue-gas multi-pollutant, are both " resource section The need for about type, environmentally friendly " social construction, the need for being also China's energy industry sustainable development.
For integrated removing sulfuldioxide, oxidizing process has more advantage.In power production process, 90-95% in coal-fired flue-gas NOx be NO, its poorly water-soluble can not be absorbed by absorbent, cause denitration efficiency relatively low, and NO2、NO3And N2The water solubilitys such as O5 It is stronger；Therefore, it is the key of denitration to realize the Quick Oxidations of NO in the gas phase.For mercury, particle mercury and oxidation state mercury can By the existing pollutant catabolic gene equipment collaboration removing such as electric cleaner and wet desulphurization, the key of demercuration is Hg0Removing, therefore, By Hg0Quick Oxidation is Hg in gas phase2+It is the emphasis for realizing demercuration.Based on oxidizing process principle, the existing pollution of thermal power plant is utilized Thing control device, and optimization is laid out to it, and then realize that multi-pollutant integration removing is economical and efficient and meets China One of developing direction of national conditions.
The content of the invention
In view of the shortcomings of the prior art, the invention provides the device of multi-pollutant in a kind of photocatalytic oxidation removing flue gas And method.
A kind of device of multi-pollutant in photocatalytic oxidation removing flue gas, flue gas pipeline 11 is communicated to electrostatic precipitator 4 Smoke inlet, the exhanst gas outlet of electrostatic precipitator 4 is communicated in absorption plant 5, flue gas pipeline 11 by pipeline 12 and sets cigarette Gas UTILIZATION OF VESIDUAL HEAT IN and mist generating device 2, the fume afterheat is utilized and mist generating device 2 uses the big inner sleeve tubule 24 of pipe 23 Structure, breach 25 is interval with the tube wall of the tubule 24, indentation, there is provided with orifice plate 26, and the orifice plate 26 is fixed on tubule On 24 inwall, its external diameter is equal to the internal diameter of tubule 24, and the entrance of tubule 24 is connected with the ＇ of air compressor system 1, the entrance of big pipe 23 It is connected with oxidant storage tank 1, the outlet of big pipe 23 is connected with the entrance of light co-catalysis priming reaction device 3, the activation of light co-catalysis The outlet of reaction unit 3 is connected to the exhanst gas outlet of electrostatic precipitator 4；The smooth co-catalysis priming reaction device 3 is cylinder knot Structure, its local array is placed with quartz ampoule 33, quartz ampoule 33 and is cased with UV lamp pipe 32；The exhanst gas outlet of absorption plant 5 is through efficient Demister is connected to chimney.
The porch of the smooth co-catalysis priming reaction device 3 is provided with conical flow distribution apparatus 31.
The cylindrical structure of the smooth co-catalysis priming reaction device 3, from outside to inside successively include steel casing, heat-insulation layer, Separation layer and anticorrosive coat.
The fume afterheat is utilized and mist generating device 2 uses titanium steel material, includes the He of coil section 21 of left and right ends The straight length 22 at middle part.
The spacing of the breach 25 is 10-15cm；The orifice plate 26 is provided with multiple holes, and voidage is 80%.
The method of the device purifying smoke of multi-pollutant in a kind of photocatalytic oxidation removing flue gas, the ＇ of air compressor system 1 to Conveying compressed air in the tubule 24 of the fume afterheat utilization and mist generating device 2, oxidant storage tank 1 is noted into big pipe 23 Enter combined oxidation agent solution, compressed air is continuously outflowed by breach 25 and into and out composite oxidant is molten into tubule 24 In liquid, compressed air constantly perturbs composite oxidant by forming violent turbulence effect in breach 25 and the flow process of orifice plate 26 Solution, makes combined oxidation agent solution form fluidized state in big pipe 23；Meanwhile, the heat smoke of thermal power plant's air preheater output is in stream During through flue gas pipeline 11, utilized with fume afterheat and mist generating device 2 exchanges heat, make the liquid phase combined oxidation in big pipe 23 Agent is atomized while boiling and becomes misty liquid droplets, and then increases gas liquid interfacial area；
It is atomized composite oxidant and enters light co-catalysis priming reaction device 3, the radiation that array UV lamp pipe 32 is produced is through interior Embedding quartz ampoule 33 carries out catalytic activation to composite oxidant, produces a variety of free radicals, and free radical is filled from light co-catalysis priming reaction The outlet for putting 3 sprays, and exhanst gas outlet and the smoke contacts into electrostatic precipitator 4 carry out multi-pollutant in-situ oxidation reaction, will NO in flue gas is changed into the NOx of high-valence state, including NO2、NO3、N2O5, by Hg0It is oxidized to Hg2+, NOx, Hg2+And SO2With flue gas Into absorption plant 5 by absorbing and removing, after high efficiency demister demisting, air is discharged into by chimney again for flue gas；
In terms of mass concentration, the complex catalyst solution is the H containing 30-50wt%2O2, 0-2wt%CH3COOOH and The mixed aqueous solution of 0.01-0.5wt% additive, the additive be in NaBr, NaCl, HBr, HCl, HF it is a kind of with On, the pH of the complex catalyst solution is 5-6；
In terms of mass concentration, absorbing liquid in absorption plant 5 for MgO, 0-5wt% containing 5-10wt% KCl and 0.5-2wt% KOH absorption slurries, the pH of absorbing liquid is 8-10.
The particle diameter of the misty liquid droplets is 50-60 μm.
The porch of the smooth co-catalysis priming reaction device 3 is provided with conical flow distribution apparatus 31, is atomized combined oxidation Agent is made atomization composite oxidant turbulization, composite oxidant is helped in light and urged by the water conservancy diversion of conical flow distribution apparatus 31 Change and be uniformly distributed in priming reaction device 3.
The composite catalyst is H2O2/ NaBr the aqueous solution：H2O2Mass concentration ratio with NaBr is (40-50):(0.01- 0.1), pH value of solution is 5.5-6；
Or the liquid phase composite catalyst is H2O2/ NaCl the aqueous solution：H2O2It is (40-50) with NaCl mass concentration ratios: (0.3-0.5), pH value of solution is 5-6；
Or the liquid phase composite catalyst is H2O2/CH3The COOOH/HBr aqueous solution：H2O2、CH3COOOH and HBr quality Concentration ratio is (30-35):(0.5-2):(0.1-0.3), pH value of solution is 5-6；
Or the liquid phase composite catalyst is H2O2/CH3The COOOH/HF aqueous solution：H2O2、CH3COOOH and HF quality is dense Degree is than being (30-35):(0.5-2):(0.05-0.2), pH value of solution is 5-5.5；
Or the liquid phase composite catalyst is H2O2/CH3COOOH/HCl：H2O2、CH3COOOH and HCl mass concentration ratio For (35-40):(1-2):(0.3-0.5), pH value of solution is 5-5.5.
The preparation process of the liquid phase composite oxidant is：By oxidant H2O2And/or CH3COOOH, with additive according to Ratio is mixed, and is then diluted to normal concentration with water.Above-mentioned a variety of composite oxidants have stronger stability, in 12h It is interior without significant gas release phenomenon, be conducive to composite oxidant prepare and its stocking system safe operation.
Working condition is as follows：
(1) fume afterheat utilize and mist generating device 2 in temperature range be 100-130 DEG C；
(2) liquid-gas ratio of composite oxidant addition and flue gas flow is the m of 10-25L/ ten thousand3；
(3) compressed air inlet pressure is 2-4kg, and the flow-rate ratio with composite oxidant is (50-150):1；
(4) radiant energy density in light co-catalysis priming reaction device 3 is 0.64-1.28KW/m3；
(5) pipeline 12 is flue gas multiple pollutant oxidation reaction section, and wherein gas residence time is 1-2s；
(6) in absorption plant 5, the liquid-gas ratio of absorbing liquid and flue gas flow is 10-15L/m3；Reaction temperature is 40~60 ℃。
Reaction mechanism of the present invention：
Hydrogen peroxide, Peracetic acid, oxygen are once oxidation agent, peroxide root, hydroxyl radical free radical, chlorine oxygen radical, bromine oxygen Free radical, fluorine oxygen radical, chlorine radical, bromine free radical, fluoro free radical, chlorine, simple substance bromine, simple substance fluoride etc. are secondary oxidation Agent, these oxidants and the Hg in flue gas0Oxidation bonding is oxidation state Hg2+, NO is oxidized to oxidation state NOx.Liquid phase composite oxygen The catalytic activation mechanism of agent and the reaction mechanism between multi-pollutant are as follows：
H2O2+hv→2HO·
CH3COOOH+hv→CH3COO·+HO·
H2O2+CH3COO·→CH3COOOH+HO·
HO·+Cl-→ClOH·-
ClOH·-+H+→Cl·+H2O
Cl·+Cl·→Cl2
HO·+Br-→BrOH·-
BrOH·-+H+→Br·+H2O
Br·+Br·→Br2
HO·+F-→FOH·-
FOH·-+H+→F·+H2O
F·+F·→F2
Reaction mechanism is as follows between once oxidation agent and secondary oxidation agent and pollutant：
H2O2+N(II)+Hg0+S(IV)→N(V)+Hg(II)+S(VI)+H2O
CH3COOOH+N(II)+Hg0+S(IV)→N(V)+Hg(II)+S(VI)+CH3COOH
HO·+N(II)+Hg0+S(IV)→N(V)+Hg(II)+S(VI)+H2O
ClOH·-+Cl·+Cl2+N(II)+Hg0+S(IV)→N(V)+Hg(II)+S(VI)+Cl-
BrOH·-+Br·+Br2+N(II)+Hg0+S(IV)→N(V)+Hg(II)+S(VI)+Br-
FOH·-+F·+F2+N(II)+Hg0+S(IV)→N(V)+Hg(II)+S(VI)+F-
Reaction mechanism is as follows between oxidation product and absorbent：
H2O+MgO+N(V)+S(VI)→MgSO4+Mg(NO3)2
K++N(V)+S(VI)→K2SO4+KNO3
Na++N(V)+S(VI)→Na2SO4+NaNO3
Hg2++ M → HgM (chemisorbed)
Wherein, M is the fine particle or other components in flue gas.
Beneficial effects of the present invention are：
1st, the inventive method is unique, using oxide of high activity component first to the NO and Hg in flue gas0Aoxidized, then Realize SO2, NOx and Hg2+While remove so that realize desulfurization denitration demercuration integration, greatly reduce grading desulfurization denitration The capital construction of demercuration and operating cost, and integrated removal efficiency is improved, simultaneous SO_2 and NO removal demercuration efficiency is as shown in table 1, Under the conditions of power plants typical case's operating condition, current fossil-fuel power plant atmospheric pollutant emission standard can be met.Compared to series connection The classification processing system of formula, the capital construction of processing system of the invention and operating cost are lower, operate more easy, and removing product is A kind of high-quality composite fertilizer, is conducive to recycling, with higher economy and environmental benefit.The gas cleaning work of the present invention The proposition of skill is a kind of useful supplement to Thermal Power Generation Industry near-zero release technical system, solves the people one existed for a long time It is straight to think solution and always unsolved problem, have broad application prospects.
The simultaneous SO_2 and NO removal demercuration effect of table 1
Project Before processing After processing Removal efficiency
Hg0Concentration 50μg/m3 2.5-4μg/m3 92-95%
NO concentration 400mg/m3 40-60mg/m3 85-90%
SO2Concentration 5000mg/m3 0-50mg/m3 99-100%
2nd, the present invention effectively make use of heat smoke waste heat, while anti-oxidant active is improved, also reduces electrostatic and removes Dirt device entrance flue gas temperature, is conducive to the control of superfine particulate matter, improves dust-collecting efficiency.
3rd, it is applicable based on fume afterheat using the integral method of the photocatalytic oxidation removing flue gas multiple pollutant of technology It is to solve one of feasible scheme of northern coal smoke type haze in a variety of Industrial Boilers.
Brief description of the drawings
Fig. 1 is that fume afterheat is utilized and mist generating device schematic diagram；
Fig. 2 is that fume afterheat is utilized and mist generating device cut-away view；
Fig. 3 is light co-catalysis priming reaction schematic device；
Fig. 4 is the device flow chart that a kind of photocatalytic oxidation removes multi-pollutant in flue gas.
Label declaration：1- oxidant storage tanks, 1 ＇-air compressor system, 2- fume afterheats are utilized and mist generating device, 3- light Co-catalysis priming reaction device, 4- electrostatic precipitator, 5- absorption plants, 11- flue gas pipelines, 12- pipelines, 21- coil sections, 22- Straight length, the big pipes of 23-, 24- tubules, 25- breach, 26- orifice plates, 31- conical flow distribution apparatus, 32-UV fluorescent tubes, 33- quartz Pipe.
Embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description.It is emphasized that the description below It is merely exemplary, the scope being not intended to be limiting of the invention and its application.
A kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas as shown in Figure 4, and flue gas pipeline 11 is communicated to quiet The smoke inlet of electric cleaner 4, the exhanst gas outlet of electrostatic precipitator 4 is communicated to absorption plant 5, flue gas pipeline 11 by pipeline 12 Interior setting fume afterheat is utilized and mist generating device 2, and as shown in Figure 1-2, the fume afterheat is utilized and mist generating device 2 Using the coil section 21 and the straight length 22 at middle part of titanium steel material, including left and right ends, it uses the big inner sleeve tubule 24 of pipe 23 10-15cm is spaced on structure, the tube wall of the tubule 24 and is provided with breach 25, indentation, there is provided with orifice plate 26, and the orifice plate 26 is fixed On the inwall of tubule 24, orifice plate 26 is provided with multiple holes, and voidage is 80%, and its external diameter is equal to the internal diameter of tubule 24, small The entrance of pipe 24 is connected with the ＇ of air compressor system 1, and the entrance of big pipe 23 is connected with oxidant storage tank 1, and the outlet of big pipe 23 is helped with light The entrance of catalytic activation reaction unit 3 is connected, and the outlet of light co-catalysis priming reaction device 3 is connected to the flue gas of electrostatic precipitator 4 Outlet；As shown in figure 3, the smooth co-catalysis priming reaction device 3 be cylindrical structure, from outside to inside successively include steel casing, Heat-insulation layer, separation layer and anticorrosive coat, plug-type mode is inserted in beyond its local array is placed with quartz ampoule 33, quartz ampoule 33 UV lamp pipe 32, and conical flow distribution apparatus 31 is provided with the porch of light co-catalysis priming reaction device 3, it is atomized combined oxidation Agent is made atomization composite oxidant turbulization, is conducive to composite oxidant in light by the water conservancy diversion of conical flow distribution apparatus 31 It is uniformly distributed in co-catalysis priming reaction device 3；The exhanst gas outlet of absorption plant 5 is connected to chimney through two-stage high efficiency demister.
Embodiment 1
Combined oxidation agent solution：H2O2Mass concentration is 50wt%, and pH is 6.
Above-mentioned liquid phase composite oxidant injection fume afterheat is utilized and mist generating device 2, activated by light co-catalysis Integration desulfurization denitration demercuration is realized after reaction unit 3, absorption plant 5, reaction condition is shown in Table 2.
Table 2
Reaction condition Scope
Temperature DEG C in fume afterheat utilization and mist generating device 110
The m of liquid-gas ratio L/ ten thousand of composite oxidant addition and flue gas flow3 20
Compressed air pressure kg 2
The flow-rate ratio of compressed air and composite oxidant 50:1
Light co-catalysis priming reaction device energy density KW/m3 1.1
Flue gas pollutant oxidation reaction section gas residence time s 1.5
MgO, KCl, KOH mass concentration ratio wt% in absorbing liquid 8:2:1
The pH of absorbing liquid 9
The liquid-gas ratio L/m of absorbing liquid and coal-fired flue-gas amount3 12
Absorption plant interior reaction temperature DEG C 50
Desulfuration demercuration denitration process is carried out to flue gas by above-mentioned condition, detection is obtained：SO2Removal efficiency be 100%, take off Nitre efficiency is 87%, and demercuration efficiency is more than 92.1%.
Embodiment 2
Combined oxidation agent solution：H2O2Mass concentration ratio with NaBr is 40:0.05, pH is 5.5.
Above-mentioned liquid phase composite oxidant injection fume afterheat is utilized and mist generating device 2, activated by light co-catalysis Integration desulfurization denitration demercuration is realized after reaction unit 3, absorption plant 5, reaction condition is shown in Table 3.
Table 3
Desulfuration demercuration denitration process is carried out to flue gas by above-mentioned condition, detection is obtained：SO2Removal efficiency be 99%, take off Nitre efficiency is 88.7%, and demercuration efficiency is more than 94.7%.
Embodiment 3
Combined oxidation agent solution：H2O2Mass concentration ratio with NaCl is 40:0.5, pH is 5.
Above-mentioned liquid phase composite oxidant injection fume afterheat is utilized and mist generating device, activated by light co-catalysis anti- Answer and integration desulfurization denitration demercuration is realized after device, absorption plant, reaction condition is shown in Table 4.
Table 4
Desulfuration demercuration denitration process is carried out to flue gas by above-mentioned condition, detection is obtained：SO2Removal efficiency be 99%, take off Nitre efficiency is 86.4%, and demercuration efficiency is more than 93.5%.
Embodiment 4
Combined oxidation agent solution：H2O2、CH3COOOH, HBr mass concentration ratio are 35:1:0.2, pH is 5.
Above-mentioned liquid phase composite oxidant injection fume afterheat is utilized and mist generating device, activated by light co-catalysis anti- Answer and integration desulfurization denitration demercuration is realized after device, absorption plant, reaction condition is shown in Table 5.
Table 5
Desulfuration demercuration denitration process is carried out to flue gas by above-mentioned condition, detection is obtained：SO2Removal efficiency be 100%, take off Nitre efficiency is 85.7%, and demercuration efficiency is more than 92.1%.
Embodiment 5
Combined oxidation agent solution：H2O2And CH3COOOH mass concentration ratio is 45:2, pH be 5.
Above-mentioned liquid phase composite oxidant injection fume afterheat is utilized and mist generating device, activated by light co-catalysis anti- Answer and integration desulfurization denitration demercuration is realized after device, absorption plant, reaction condition is shown in Table 6.
Table 6
Reaction condition Scope
Temperature DEG C in fume afterheat utilization and mist generating device 100
The m of liquid-gas ratio L/ ten thousand of composite oxidant addition and exhaust gas volumn3 18
Compressed air pressure kg 2
The flow-rate ratio of compressed air and composite oxidant 120:1
Light co-catalysis priming reaction device energy density KW/m3 1.2
Flue gas pollutant oxidation reaction section gas residence time s 2
MgO, KCl, KOH mass concentration ratio wt% in absorbing liquid 6:4:0.5
The pH of absorbing liquid 8.5
The liquid-gas ratio L/m of absorbing liquid and coal-fired flue-gas amount3 15
Absorption plant interior reaction temperature DEG C 50
Desulfuration demercuration denitration process is carried out to flue gas by above-mentioned condition, detection is obtained：SO2Removal efficiency be 99.7%, Denitration efficiency is 88.9%, and demercuration efficiency is more than 92%.
Embodiment 6
Combined oxidation agent solution：H2O2、CH3COOOH, HF mass concentration ratio are 30:1:0.1, pH is 5.5.
Above-mentioned liquid phase composite oxidant injection fume afterheat is utilized and mist generating device, activated by light co-catalysis anti- Answer and integration desulfurization denitration demercuration is realized after device, absorption plant, reaction condition is shown in Table 7.
Table 7
Reaction condition Scope
Temperature DEG C in fume afterheat utilization and mist generating device 115
The m of liquid-gas ratio L/ ten thousand of composite oxidant addition and exhaust gas volumn3 15
Compressed air pressure kg 4
The flow-rate ratio of compressed air and composite oxidant 50
Light co-catalysis priming reaction device energy density KW/m3 0.9
Flue gas pollutant oxidation reaction section gas residence time s 2
MgO, KCl, KOH mass concentration ratio wt% in absorbing liquid 10:0:1
The pH of absorbing liquid 8.5
The liquid-gas ratio L/m of absorbing liquid and coal-fired flue-gas amount3 15
Absorption plant interior reaction temperature DEG C 60
Desulfuration demercuration denitration process is carried out to flue gas by above-mentioned condition, detection is obtained：SO2Removal efficiency be 100%, take off Nitre efficiency is 86.8%, and demercuration efficiency is more than 93.9%.
Embodiment 7
Combined oxidation agent solution：H2O2、CH3COOOH, HCl mass concentration ratio are 40:1.5:0.5, pH is 5.5.
Above-mentioned liquid phase composite oxidant injection fume afterheat is utilized and mist generating device, activated by light co-catalysis anti- Answer and integration desulfurization denitration demercuration is realized after device, absorption plant, reaction condition is shown in Table 8.
Table 8
Reaction condition Scope
Temperature DEG C in fume afterheat utilization and mist generating device 100
The m of liquid-gas ratio L/ ten thousand of composite oxidant addition and exhaust gas volumn3 10
Compressed air pressure kg 4
The flow-rate ratio of compressed air and composite oxidant 150
Light co-catalysis priming reaction device energy density KW/m3 1.28
Flue gas pollutant oxidation reaction section gas residence time s 1
MgO, KCl, KOH mass concentration ratio wt% in absorbing liquid 5:5:1
The pH of absorbing liquid 9.5
The liquid-gas ratio L/m of absorbing liquid and coal-fired flue-gas amount3 15
Absorption plant interior reaction temperature DEG C 50
Desulfuration demercuration denitration process is carried out to flue gas by above-mentioned condition, detection is obtained：SO2Removal efficiency be 99%, take off Nitre efficiency is 89.54%, and demercuration efficiency is more than 92.9%.

Claims (9)

1. a kind of device of multi-pollutant in photocatalytic oxidation removing flue gas, flue gas pipeline (11) is communicated to electrostatic precipitator (4) smoke inlet, the exhanst gas outlet of electrostatic precipitator (4) is communicated to absorption plant (5) by pipeline (12), and its feature exists In setting fume afterheat is utilized and mist generating device (2) in flue gas pipeline (11), and the fume afterheat is utilized and atomization occurs Device (2) uses and is interval with breach (25) on the structure of big pipe (23) inner sleeve tubule (24), the tube wall of the tubule (24), lacks Orifice plate (26) is provided with mouthful, the orifice plate (26) is fixed on the inwall of tubule (24), its external diameter is equal to the internal diameter of tubule (24), The entrance of tubule (24) is connected with air compressor system (1 ＇), and the entrance of big pipe (23) is connected with oxidant storage tank (1), big pipe (23) Outlet be connected with the entrance of light co-catalysis priming reaction device (3), the outlet of light co-catalysis priming reaction device (3) is connected to The exhanst gas outlet of electrostatic precipitator (4)；The smooth co-catalysis priming reaction device (3) is cylindrical structure, the arrangement of its local array Have in quartz ampoule (33), quartz ampoule (33) and be cased with UV lamp pipe (32)；The exhanst gas outlet of absorption plant (5) is connected through high efficiency demister To chimney.
2. a kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas according to claim 1, it is characterised in that institute The porch for stating light co-catalysis priming reaction device (3) is provided with conical flow distribution apparatus (31).
3. a kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas according to claim 1, it is characterised in that institute State the cylindrical structure of light co-catalysis priming reaction device (3), from outside to inside successively include steel casing, heat-insulation layer, separation layer and Anticorrosive coat.
4. a kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas according to claim 1, it is characterised in that institute State that fume afterheat is utilized and mist generating device (2) uses titanium steel material, include coil section (21) and the middle part of left and right ends Straight length (22).
5. a kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas according to claim 1, it is characterised in that institute The spacing for stating breach (25) is 10-15cm；The orifice plate (26) is provided with multiple holes, and porosity is 80%.
6. the device purification of multi-pollutant in a kind of photocatalytic oxidation removing flue gas described in claim 1-5 any claims The method of flue gas, it is characterised in that air compressor system (1 ＇) to the fume afterheat utilize and mist generating device (2) tubule (24) injection combined oxidation agent solution in conveying compressed air, oxidant storage tank (1) Xiang great Guan (23) in, compressed air is by breach (25) continuously outflow and into tubule (24) in into and out combined oxidation agent solution, compressed air by breach (25) and Turbulence effect is formed in orifice plate (26) flow process, combined oxidation agent solution is constantly perturbed, combined oxidation agent solution is managed greatly (23) fluidized state is formed in；Meanwhile, heat smoke is utilized and is atomized when flowing through flue gas pipeline (11), with fume afterheat and fills Put (2) to exchange heat, the composite oxidant in big pipe (23) is atomized while boiling and is become misty liquid droplets, Jin Erzeng Big gas liquid interfacial area；
It is atomized composite oxidant and enters light co-catalysis priming reaction device (3), the radiation that array UV lamp pipe (32) is produced is through interior Embedding quartz ampoule (33) carries out catalytic activation to composite oxidant and produces a variety of free radicals, and free radical is filled from light co-catalysis priming reaction The outlet for putting (3) sprays, and exhanst gas outlet and smoke contacts the progress multi-pollutant in-situ oxidation into electrostatic precipitator (4) are anti- Should, the NO in flue gas is changed into the NOx of high-valence state, by Hg0It is oxidized to Hg2+, NOx, Hg2+And SO2Enter to absorb with flue gas and fill (5) are put by absorbing and removing, after high efficiency demister demisting, air is discharged into by chimney again for flue gas；
In terms of mass concentration, the combined oxidation agent solution is the H containing 30-50wt%2O2, 0-2wt%CH3COOOH and 0- The mixed aqueous solution of 0.5wt% additive, the additive is one or more of NaBr, NaCl, HBr, HCl, HF, described The pH of combined oxidation agent solution is 5-6；
In terms of mass concentration, the absorbing liquid in absorption plant (5) is the KCl and 0.5- of MgO, 0-5wt% containing 5-10wt% 2wt% KOH absorption slurries, the pH of absorbing liquid is 8-10.
7. a kind of photocatalytic oxidation removes the side of the device purifying smoke of multi-pollutant in flue gas according to claim 6 Method, it is characterised in that the particle diameter of the misty liquid droplets is 50-60 μm.
8. a kind of photocatalytic oxidation removes the side of the device purifying smoke of multi-pollutant in flue gas according to claim 6 Method, it is characterised in that the porch of the smooth co-catalysis priming reaction device (3) is provided with conical flow distribution apparatus (31), mist Change composite oxidant by conical flow distribution apparatus (31) water conservancy diversion, make atomization composite oxidant turbulization, make composite oxygen Agent is uniformly distributed in light co-catalysis priming reaction device (3).
9. a kind of photocatalytic oxidation removes the side of the device purifying smoke of multi-pollutant in flue gas according to claim 6 Method, it is characterised in that the composite oxidant is H2O2/ NaBr the aqueous solution：H2O2Mass concentration ratio with NaBr is (40-50): (0.01-0.1), pH value of solution is 5.5-6；
Or the composite oxidant is H2O2/ NaCl the aqueous solution：H2O2It is (40-50) with NaCl mass concentration ratios:(0.3-0.5), PH value of solution is 5-6；
Or the composite oxidant is H2O2/CH3The COOOH/HBr aqueous solution：H2O2、CH3COOOH and HBr mass concentration ratio is (30-35):(0.5-2):(0.1-0.3), pH value of solution is 5-6；
Or the composite oxidant is H2O2/CH3The COOOH/HF aqueous solution：H2O2、CH3COOOH and HF mass concentration ratio is (30-35):(0.5-2):(0.05-0.2), pH value of solution is 5-5.5；
Or the composite oxidant is H2O2/CH3COOOH/HCl：H2O2、CH3COOOH and HCl mass concentration ratio is (35- 40):(1-2):(0.3-0.5), pH value of solution is 5-5.5.
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