CN105536466A - Device and method for removing various pollutants in flue gas through photoassisted catalytic oxidization - Google Patents

Device and method for removing various pollutants in flue gas through photoassisted catalytic oxidization Download PDF

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CN105536466A
CN105536466A CN201610049882.XA CN201610049882A CN105536466A CN 105536466 A CN105536466 A CN 105536466A CN 201610049882 A CN201610049882 A CN 201610049882A CN 105536466 A CN105536466 A CN 105536466A
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flue gas
catalysis
pollutant
composite
reaction device
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CN105536466B (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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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Abstract

The invention relates to a device and method for removing various pollutants in flue gas through photoassisted catalytic oxidization. Flue gas waste heat utilizing and atomizing generation device is arranged in a pipeline between an air pre-heater and an electrostatic dust remover and is of a structure that a small pipe is sleeved with a large pipe; the large pipe is used for conveying a composite oxidization agent; compressed air in the small pipe makes the composite oxidization agent in a boiling state; meanwhile, hot flue gas and the composite oxidization agent exchange heat so that the composite oxidization agent can be atomized into ultrafine liquid drops; the atomized composite oxidization agent enters a photoassisted catalysis and activation reaction device to be catalyzed and activated, various free radicals are generated and ejected out of an outlet of the photoassisted catalysis and activation reaction device and make contact with flue gas with dust removed, NO in the flue gas is converted into high-valence-state NOx, HgO is oxidized into Hg2+, NOx, Hg2+ and SO2 enter an absorbing device along with the flue gas and are absorbed and removed, efficient and synergistic desulfurization, denitration and mercury removal are achieved, removed products are high-quality compound fertilizer, resource utilization is facilitated, and high economic and environmental benefits are achieved.

Description

A kind of photocatalytic oxidation removes the device and method of multi-pollutant in flue gas
Technical field
The invention belongs to flue gases purification field, particularly a kind of photocatalytic oxidation removes the device and method of multi-pollutant in flue gas.
Background technology
China's atmosphere pollution belongs to typical coal-smoke pollution, wherein sulfur dioxide, nitrogen oxide and heavy metal are the significant pollutants of coal-fired flue-gas, sulfur dioxide and nitrogen oxide are the main sources of acid rain, nitrogen oxide is also one of the main predecessor forming photochemical fog, and Elemental Mercury has strong toxicity, form stable and the feature of difficult for biological degradation.In recent years, because in coal-fired flue-gas, the discharge capacity of sulfur dioxide, nitrogen oxide and heavy metal significantly improves, China's haze is caused to take place frequently, serious harm people ' s health and ecological environment.
The main flume desulfur technology that coal-burning power plant of China adopts is Wet Limestone-plastering (WFGD), this technique possesses skills the advantages such as maturation, desulfuration efficiency is higher, coal accommodation is wide, smoke treatment amount is large, but there is system complex, the high deficiency of energy consumption, and the desulfuration efficiency of 95% cannot meet regional especially 50mg/m 3concentration of emission limit value.And traditional SCR catalyst exists cost is high, the life-span is short problem, and the escaping of ammonia, catalyst poisoning and the waste catalyst bottleneck also becoming SCR denitration technical development such as difficult.There is high, the discarded active carbon of cost and be difficult to the problems such as recycling in charcoal absorption demercuration method.Simultaneously, this classification processing mode have that floor space is large, system run all right is poor, equipment energy consumption is higher and the problems such as secondary pollution therefore, therefore, research and develop emerging coal-fired flue-gas multi-pollutant integration removing sulfuldioxide, be the needs of " resource-conserving, environmentally friendly " social construction, the needs of Ye Shi China energy industry sustainable development.
With regard to integrated removing sulfuldioxide, oxidizing process has more advantage.In power production process, in coal-fired flue-gas, the NOx of 90-95% is NO, and its poorly water-soluble cannot be absorbed by absorbent, causes denitration efficiency lower, and NO 2, NO 3and N 2o5 etc. are water-soluble stronger; Therefore, the key that NO Quick Oxidation is in the gas phase denitration is realized.For mercury, particle mercury and oxidation state mercury can be removed by the existing pollutant catabolic gene equipment collaboration such as electric cleaner and wet desulphurization, and the key of demercuration is Hg 0remove, therefore, by Hg 0in gas phase, Quick Oxidation is Hg 2+it is the emphasis realizing demercuration.Based on oxidizing process principle, utilize the existing pollutant catabolic gene device of thermal power plant, and layout optimization is carried out to it, and then realize multi-pollutant integration and remove and be economical and efficient and one of developing direction tallied with the national condition.
Summary of the invention
Not enough for prior art, the invention provides the device and method that a kind of photocatalytic oxidation removes multi-pollutant in flue gas.
A kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas, flue gas pipeline 11 is communicated to the smoke inlet of electrostatic precipitator 4, the exhanst gas outlet of electrostatic precipitator 4 is communicated to absorption plant 5 by pipeline 12, arrange fume afterheat in flue gas pipeline 11 to utilize and mist generating device 2, described fume afterheat utilization and mist generating device 2 adopt the structure of bassoon 23 inner sleeve tubule 24, the tube wall of described tubule 24 is interval with breach 25, indentation, there is provided with orifice plate 26, described orifice plate 26 is fixed on the inwall of tubule 24, its external diameter equals the internal diameter of tubule 24, the entrance of tubule 24 is connected with air compressor system 1 ＇, the entrance of bassoon 23 is connected with oxidant storage tank 1, the outlet of bassoon 23 is 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, described smooth co catalysis priming reaction device 3 is cylindrical structure, and its local array is placed with quartz ampoule 33, and quartz ampoule 33 inner sleeve has UV fluorescent tube 32, the exhanst gas outlet of absorption plant 5 is connected to chimney through high efficiency demister.
The porch of described smooth co catalysis priming reaction device 3 is provided with conical flow distribution apparatus 31.
The cylindrical structure of described smooth co catalysis priming reaction device 3, comprises steel casing, heat-insulation layer, separation layer and anticorrosive coat from outside to inside successively.
Described fume afterheat utilizes and mist generating device 2 adopts titanium steel material, comprises the coil section 21 at two ends, left and right and the straight length 22 at middle part.
The spacing of described breach 25 is 10-15cm; Described orifice plate 26 is provided with multiple hole, and voidage is 80%.
A kind of photocatalytic oxidation removes the method for the device purifying smoke of multi-pollutant in flue gas, air compressor system 1 ＇ to described fume afterheat utilize and mist generating device 2 tubule 24 in carry compressed air, oxidant storage tank 1 injects combined oxidation agent solution in bassoon 23, compressed air continuously outflows and enters tubule 24 by breach 25 and enters or flow out in combined oxidation agent solution, compressed air is by forming violent turbulence effect in breach 25 and orifice plate 26 flow process, constantly perturb combined oxidation agent solution, combined oxidation agent solution is made to form fluidized state in bassoon 23, simultaneously, the heat smoke that thermal power plant air preheater exports, when flowing through flue gas pipeline 11, to utilize with fume afterheat and heat exchange occurs mist generating device 2, makes liquid phase composite oxidant in bassoon 23 while seething with excitement, be atomized and become misty liquid droplets, and then increasing gas liquid interfacial area,
Atomization composite oxidant enters light co catalysis priming reaction device 3, the embedded quartz ampoule 33 pairs of composite oxidants that are radiated through that array UV fluorescent tube 32 produces carry out catalytic activation, produce multiple free radical, free radical sprays from the outlet of light co catalysis priming reaction device 3, the exhanst gas outlet and the smoke contacts that enter electrostatic precipitator 4 carry out the reaction of multi-pollutant in-situ oxidation, NO in flue gas is changed into the NOx of high-valence state, comprise NO 2, NO 3, N 2o 5, by Hg 0be oxidized to Hg 2+, NOx, Hg 2+and SO 2enter absorption plant 5 by absorbing and removing with flue gas, flue gas after high efficiency demister demist, enters air by chimney again;
In mass concentration, described complex catalyst solution is the H containing 30-50wt% 2o 2, 0-2wt%CH 3the mixed aqueous solution of the additive of COOOH and 0.01-0.5wt%, described additive is more than one in NaBr, NaCl, HBr, HCl, HF, and the pH of described complex catalyst solution is 5-6;
In mass concentration, the absorbing liquid in absorption plant 5 is the absorption slurries of the KOH of KCl and 0.5-2wt% of MgO, 0-5wt% containing 5-10wt%, and the pH of absorbing liquid is 8-10.
The particle diameter of described misty liquid droplets is 50-60 μm.
The porch of described smooth co catalysis priming reaction device 3 is provided with conical flow distribution apparatus 31, atomization composite oxidant is by described conical flow distribution apparatus 31 water conservancy diversion, make atomization composite oxidant turbulization, composite oxidant is uniformly distributed in light co catalysis priming reaction device 3.
Described composite catalyst is H 2o 2/ NaBr the aqueous solution: H 2o 2be (40-50) with the mass concentration ratio of NaBr: (0.01-0.1), pH value of solution is 5.5-6;
Or described liquid phase composite catalyst is H 2o 2/ NaCl the aqueous solution: H 2o 2be (40-50) with NaCl mass concentration ratio: (0.3-0.5), pH value of solution is 5-6;
Or described liquid phase composite catalyst is H 2o 2/ CH 3the COOOH/HBr aqueous solution: H 2o 2, CH 3the mass concentration ratio of COOOH and HBr is (30-35): (0.5-2): (0.1-0.3), and pH value of solution is 5-6;
Or described liquid phase composite catalyst is H 2o 2/ CH 3the COOOH/HF aqueous solution: H 2o 2, CH 3the mass concentration ratio of COOOH and HF is (30-35): (0.5-2): (0.05-0.2), and pH value of solution is 5-5.5;
Or described liquid phase composite catalyst is H 2o 2/ CH 3cOOOH/HCl:H 2o 2, CH 3the mass concentration ratio of COOOH and HCl is (35-40): (1-2): (0.3-0.5), and pH value of solution is 5-5.5.
The preparation process of described liquid phase composite oxidant is: by oxidant H 2o 2and/or CH 3cOOOH, proportionally mixes with additive, is then diluted to normal concentration with water.Above-mentioned multiple composite oxidant has stronger stability, without significant air release phenomenon in 12h, is conducive to the safe operation of composite oxidant preparation and stocking system thereof.
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 10-25L/ ten thousand m 3;
(3) compressed air inlet pressure is 2-4kg, is (50-150): 1 with the flow-rate ratio of composite oxidant;
(4) radiant energy density in light co catalysis priming reaction device 3 is 0.64-1.28KW/m 3;
(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/m 3; Reaction temperature is 40 ~ 60 DEG C.
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 radical, fluorine oxygen radical, chlorine radical, bromine free radical, fluoro free radical, chlorine, simple substance bromine, simple substance fluoride etc. are secondary oxidation agent, the Hg in these oxidants and flue gas 0oxidation bonding is oxidation state Hg 2+, NO is oxidized to oxidation state NOx.The catalytic activation mechanism of liquid phase composite oxidant and and multi-pollutant between reaction mechanism as follows:
H 2O 2+hv→2HO·
CH 3COOOH+hv→CH 3COO·+HO·
H 2O 2+CH 3COO·→CH 3COOOH+HO·
HO·+Cl -→ClOH· -
ClOH· -+H +→Cl·+H 2O
Cl·+Cl·→Cl 2
HO·+Br -→BrOH· -
BrOH· -+H +→Br·+H 2O
Br·+Br·→Br 2
HO·+F -→FOH· -
FOH· -+H +→F·+H 2O
F·+F·→F 2
Once oxidation agent and between secondary oxidation agent and pollutant reaction mechanism as follows:
H 2O 2+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+H 2O
CH 3COOOH+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+CH 3COOH
HO·+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+H 2O
ClOH· -+Cl ·+Cl 2+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+Cl -
BrOH· -+Br ·+Br2+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+Br -
FOH· -+F ·+F 2+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+F -
Between oxidation product and absorbent, reaction mechanism is as follows:
H 2O+MgO+N(V)+S(VI)→MgSO 4+Mg(NO 3) 2
K ++N(V)+S(VI)→K 2SO 4+KNO 3
Na ++N(V)+S(VI)→Na2SO 4+NaNO 3
Hg 2++ M → HgM (chemisorbed)
Wherein, M is fine particle in flue gas or other components.
Beneficial effect of the present invention is:
1, the inventive method is unique, utilizes oxide of high activity component first to NO and Hg in flue gas 0be oxidized, then realize SO 2, NOx and Hg 2+while remove, thus realize desulfurization denitration demercuration integration, greatly reduce capital construction and the operating cost of grading desulfurization denitration demercuration, and improve integrated removal efficiency, simultaneous SO_2 and NO removal demercuration efficiency is as shown in table 1, under power plants typical case operating condition condition, current fossil-fuel power plant atmospheric pollutant emission standard can be met.Compared to in-line classification treatment system, capital construction and the operating cost for the treatment of system of the present invention are lower, operate more easy, and removing product is a kind of high-quality composite fertilizer, is conducive to recycling, has higher economy and environment benefit.The proposition of flue gas purifying technique of the present invention is a kind of useful supplement to Thermal Power Generation Industry near-zero release technical system, solves the people existed for a long time and wants to solve and a unsolved difficult problem always always, have broad application prospects.
Table 1 simultaneous SO_2 and NO removal demercuration effect
Project Before process After process Removal efficiency
Hg 0Concentration 50μg/m 3 2.5-4μg/m 3 92-95％
NO concentration 400mg/m 3 40-60mg/m 3 85-90％
SO 2Concentration 5000mg/m 3 0-50mg/m 3 99-100％
2, the present invention effectively make use of heat smoke waste heat, while raising anti-oxidant active, also reduces electrostatic precipitator entrance flue gas temperature, is conducive to the control of superfine particulate matter, improves dust-collecting efficiency.
3, the integral method utilizing the photocatalytic oxidation of technology to remove flue gas multiple pollutant based on fume afterheat is applicable to multiple Industrial Boiler, is one of feasible scheme solving northern coal smoke type haze.
Accompanying drawing explanation
Fig. 1 is that fume afterheat utilizes and mist generating device schematic diagram;
Fig. 2 is that fume afterheat utilizes and mist generating device cut-away view;
Fig. 3 is light co catalysis priming reaction device schematic diagram;
Fig. 4 is the device flow chart that a kind of photocatalytic oxidation removes multi-pollutant in flue gas.
Label declaration: 1-oxidant storage tank, 1 ＇-air compressor system, 2-fume afterheat utilizes and mist generating device, 3-light co catalysis priming reaction device, 4-electrostatic precipitator, 5-absorption plant, 11-flue gas pipeline, 12-pipeline, 21-coil section, 22-straight length, 23-bassoon, 24-tubule, 25-breach, 26-orifice plate, 31-conical flow distribution apparatus, 32-UV fluorescent tube, 33-quartz ampoule.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.It is emphasized that following explanation is only exemplary, instead of in order to limit the scope of the invention and apply.
A kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas as shown in Figure 4, flue gas pipeline 11 is communicated to the smoke inlet of electrostatic precipitator 4, the exhanst gas outlet of electrostatic precipitator 4 is communicated to absorption plant 5 by pipeline 12, arrange fume afterheat in flue gas pipeline 11 to utilize and mist generating device 2, as shown in Figure 1-2, described fume afterheat utilizes and mist generating device 2 adopts titanium steel material, comprise the coil section 21 at two ends, left and right and the straight length 22 at middle part, it adopts the structure of bassoon 23 inner sleeve tubule 24, on the tube wall of described tubule 24, interval 10-15cm is provided with breach 25, indentation, there is provided with orifice plate 26, described orifice plate 26 is fixed on the inwall of tubule 24, orifice plate 26 is provided with multiple hole, voidage is 80%, and its external diameter equals the internal diameter of tubule 24, the entrance of tubule 24 is connected with air compressor system 1 ＇, the entrance of bassoon 23 is connected with oxidant storage tank 1, the outlet of bassoon 23 is 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 electrostatic precipitator 4 exhanst gas outlet, as shown in Figure 3, described smooth co catalysis priming reaction device 3 is cylindrical structure, comprise steel casing, heat-insulation layer, separation layer and anticorrosive coat successively from outside to inside, its local array is placed with quartz ampoule 33, beyond in quartz ampoule 33, plug-type mode is inserted in UV fluorescent tube 32, and be provided with conical flow distribution apparatus 31 in the porch of light co catalysis priming reaction device 3, atomization composite oxidant is by described conical flow distribution apparatus 31 water conservancy diversion, make atomization composite oxidant turbulization, be conducive to composite oxidant and be uniformly distributed in light 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: H 2o 2mass concentration is 50wt%, pH is 6.
Above-mentioned liquid phase composite oxidant is injected fume afterheat utilize and mist generating device 2, after light co catalysis priming reaction device 3, absorption plant 5, realize integration desulfurization denitration demercuration, reaction condition is in table 2.
Table 2
Reaction condition Scope
Fume afterheat utilize and mist generating device in temperature DEG C 110
Liquid-gas ratio L/ ten thousand m of composite oxidant addition and flue gas flow 3 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/m 3 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 amount 3 12
Absorption plant interior reaction temperature DEG C 50
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 87%, and demercuration efficiency is more than 92.1%.
Embodiment 2
Combined oxidation agent solution: H 2o 2be 40:0.05, pH with the mass concentration ratio of NaBr be 5.5.
Above-mentioned liquid phase composite oxidant is injected fume afterheat utilize and mist generating device 2, after light co catalysis priming reaction device 3, absorption plant 5, realize integration desulfurization denitration demercuration, reaction condition is in table 3.
Table 3
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 99%, denitration efficiency is 88.7%, and demercuration efficiency is more than 94.7%.
Embodiment 3
Combined oxidation agent solution: H 2o 2be 40:0.5, pH with the mass concentration ratio of NaCl be 5.
Above-mentioned liquid phase composite oxidant is injected fume afterheat utilize and mist generating device, after light co catalysis priming reaction device, absorption plant, realize integration desulfurization denitration demercuration, reaction condition is in table 4.
Table 4
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 99%, denitration efficiency is 86.4%, and demercuration efficiency is more than 93.5%.
Embodiment 4
Combined oxidation agent solution: H 2o 2, CH 3cOOOH, HBr mass concentration ratio is 35:1:0.2, pH is 5.
Above-mentioned liquid phase composite oxidant is injected fume afterheat utilize and mist generating device, after light co catalysis priming reaction device, absorption plant, realize integration desulfurization denitration demercuration, reaction condition is in table 5.
Table 5
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 85.7%, and demercuration efficiency is more than 92.1%.
Embodiment 5
Combined oxidation agent solution: H 2o 2and CH 3the mass concentration ratio of COOOH is 45:2, pH is 5.
Above-mentioned liquid phase composite oxidant is injected fume afterheat utilize and mist generating device, after light co catalysis priming reaction device, absorption plant, realize integration desulfurization denitration demercuration, reaction condition is in table 6.
Table 6
Reaction condition Scope
Fume afterheat utilize and mist generating device in temperature DEG C 100
Liquid-gas ratio L/ ten thousand m of composite oxidant addition and exhaust gas volumn 3 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/m 3 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 amount 3 15
Absorption plant interior reaction temperature DEG C 50
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 99.7%, denitration efficiency is 88.9%, and demercuration efficiency is more than 92%.
Embodiment 6
Combined oxidation agent solution: H 2o 2, CH 3the mass concentration ratio of COOOH, HF is 30:1:0.1, pH is 5.5.
Above-mentioned liquid phase composite oxidant is injected fume afterheat utilize and mist generating device, after light co catalysis priming reaction device, absorption plant, realize integration desulfurization denitration demercuration, reaction condition is in table 7.
Table 7
Reaction condition Scope
Fume afterheat utilize and mist generating device in temperature DEG C 115
Liquid-gas ratio L/ ten thousand m of composite oxidant addition and exhaust gas volumn 3 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/m 3 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 amount 3 15
Absorption plant interior reaction temperature DEG C 60
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 86.8%, and demercuration efficiency is more than 93.9%.
Embodiment 7
Combined oxidation agent solution: H 2o 2, CH 3the mass concentration ratio of COOOH, HCl is 40:1.5:0.5, pH is 5.5.
Above-mentioned liquid phase composite oxidant is injected fume afterheat utilize and mist generating device, after light co catalysis priming reaction device, absorption plant, realize integration desulfurization denitration demercuration, reaction condition is in table 8.
Table 8
Reaction condition Scope
Fume afterheat utilize and mist generating device in temperature DEG C 100
Liquid-gas ratio L/ ten thousand m of composite oxidant addition and exhaust gas volumn 3 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/m 3 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 amount 3 15
Absorption plant interior reaction temperature DEG C 50
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 99%, denitration efficiency is 89.54%, and demercuration efficiency is more than 92.9%.

Claims (10)

1. a photocatalytic oxidation removes the device of multi-pollutant in flue gas, flue gas pipeline (11) is communicated to the smoke inlet of electrostatic precipitator (4), the exhanst gas outlet of electrostatic precipitator (4) is communicated to absorption plant (5) by pipeline (12), it is characterized in that, arrange fume afterheat in flue gas pipeline (11) to utilize and mist generating device (2), described fume afterheat utilization and mist generating device (2) adopt the structure of bassoon (23) inner sleeve tubule (24), the tube wall of described tubule (24) is interval with breach (25), indentation, there is provided with orifice plate (26), described orifice plate (26) is fixed on the inwall of tubule (24), its external diameter equals the internal diameter of tubule (24), the entrance of tubule (24) is connected with air compressor system (1 ＇), the entrance of bassoon (23) is connected with oxidant storage tank (1), the outlet of bassoon (23) is 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), described smooth co catalysis priming reaction device (3) is cylindrical structure, and its local array is placed with quartz ampoule (33), and quartz ampoule (33) inner sleeve has UV fluorescent tube (32), the exhanst gas outlet of absorption plant (5) is connected to chimney through high efficiency demister.
2. a kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas according to claim 1, it is characterized in that, the porch of described smooth 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 characterized in that, the cylindrical structure of described smooth co catalysis priming reaction device (3), comprises steel casing, heat-insulation layer, separation layer and anticorrosive coat from outside to inside successively.
4. a kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas according to claim 1, it is characterized in that, described fume afterheat utilizes and mist generating device (2) adopts titanium steel material, comprises the coil section (21) at two ends, left and right and the straight length (22) at middle part.
5. a kind of photocatalytic oxidation removes the device of multi-pollutant in flue gas according to claim 1, it is characterized in that, the spacing of described breach (25) is 10-15cm; Described orifice plate (26) is provided with multiple hole, and voidage is 80%.
6. described in the arbitrary claim of claim 1-5, a kind of photocatalytic oxidation removes the method for the device purifying smoke of multi-pollutant in flue gas, it is characterized in that, air compressor system (1 ＇) to described fume afterheat utilize and mist generating device (2) tubule (24) in conveying compressed air, oxidant storage tank (1) injects combined oxidation agent solution in bassoon (23), compressed air continuously outflows and enters tubule (24) by breach (25) and enters or flow out in combined oxidation agent solution, compressed air is by forming turbulence effect in breach (25) and orifice plate (26) flow process, constantly perturb combined oxidation agent solution, combined oxidation agent solution is made to form fluidized state in bassoon (23), simultaneously, heat smoke is when flowing through flue gas pipeline (11), to utilize with fume afterheat and heat exchange occurs mist generating device (2), make the liquid phase composite oxidant in bassoon (23) be atomized while boiling and become misty liquid droplets, and then increase gas liquid interfacial area,
Atomization composite oxidant enters light co catalysis priming reaction device (3), what array UV fluorescent tube (32) produced be radiated through, and embedded quartz ampoule (33) carries out catalytic activation to composite oxidant produces multiple free radical, free radical sprays from the outlet of light co catalysis priming reaction device (3), the exhanst gas outlet and the smoke contacts that enter electrostatic precipitator (4) carry out the reaction of multi-pollutant in-situ oxidation, NO in flue gas is changed into the NOx of high-valence state, by Hg 0be oxidized to Hg 2+, NOx, Hg 2+and SO 2enter absorption plant (5) by absorbing and removing with flue gas, flue gas after high efficiency demister demist, enters air by chimney again;
In mass concentration, described complex catalyst solution is the H containing 30-50wt% 2o 2, 0-2wt%CH 3the mixed aqueous solution of the additive of COOOH and 0-0.5wt%, described additive is more than one in NaBr, NaCl, HBr, HCl, HF, and the pH of described complex catalyst solution is 5-6;
In mass concentration, the absorbing liquid in absorption plant (5) is the absorption slurries of the KOH of KCl and 0.5-2wt% of MgO, 0-5wt% containing 5-10wt%, and the pH of absorbing liquid is 8-10.
7. a kind of photocatalytic oxidation removes the method for the device purifying smoke of multi-pollutant in flue gas according to claim 6, it is characterized in that, the particle diameter of described misty liquid droplets is 50-60 μm.
8. a kind of photocatalytic oxidation removes the method for the device purifying smoke of multi-pollutant in flue gas according to claim 6, it is characterized in that, the porch of described smooth co catalysis priming reaction device (3) is provided with conical flow distribution apparatus (31), atomization composite oxidant is by described conical flow distribution apparatus (31) water conservancy diversion, make atomization composite oxidant turbulization, composite oxidant is uniformly distributed in light co catalysis priming reaction device (3).
9. a kind of photocatalytic oxidation removes the method for the device purifying smoke of multi-pollutant in flue gas according to claim 6, it is characterized in that, described composite catalyst is H 2o 2/ NaBr the aqueous solution: H 2o 2be (40-50) with the mass concentration ratio of NaBr: (0.01-0.1), pH value of solution is 5.5-6;
Or described liquid phase composite catalyst is H 2o 2/ NaCl the aqueous solution: H 2o 2be (40-50) with NaCl mass concentration ratio: (0.3-0.5), pH value of solution is 5-6;
Or described liquid phase composite catalyst is H 2o 2/ CH 3the COOOH/HBr aqueous solution: H 2o 2, CH 3the mass concentration ratio of COOOH and HBr is (30-35): (0.5-2): (0.1-0.3), and pH value of solution is 5-6;
Or described liquid phase composite catalyst is H 2o 2/ CH 3the COOOH/HF aqueous solution: H 2o 2, CH 3the mass concentration ratio of COOOH and HF is (30-35): (0.5-2): (0.05-0.2), and pH value of solution is 5-5.5;
Or described liquid phase composite catalyst is H 2o 2/ CH 3cOOOH/HCl:H 2o 2, CH 3the mass concentration ratio of COOOH and HCl is (35-40): (1-2): (0.3-0.5), and pH value of solution is 5-5.5.
10. a kind of photocatalytic oxidation removes the method for the device purifying smoke of multi-pollutant in flue gas according to claim 6, and it is characterized in that, 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 10-25L/ ten thousand m 3;
(3) compressed air inlet pressure is 2-4kg, is (50-150): 1 with the flow-rate ratio of composite oxidant;
(4) radiant energy density in light co catalysis priming reaction device (3) is 0.64-1.28KW/m 3;
(5) pipeline (12) interior 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/m 3; Reaction temperature is 40 ~ 60 DEG C.
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