CN105032142A - Flue gas integration removal system and method by means of gas-like phase preoxidation combining with absorption - Google Patents

Flue gas integration removal system and method by means of gas-like phase preoxidation combining with absorption Download PDF

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CN105032142A
CN105032142A CN201510434927.0A CN201510434927A CN105032142A CN 105032142 A CN105032142 A CN 105032142A CN 201510434927 A CN201510434927 A CN 201510434927A CN 105032142 A CN105032142 A CN 105032142A
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gas
composite oxidant
phase composite
oxidation
phase
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CN105032142B (en
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赵毅
郝润龙
周思涵
郭天祥
杨硕
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North China Electric Power University
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Abstract

The invention belongs to the technical field of flue gas purification, and particularly relates to a flue gas integration removal system and method by means of gas-like phase preoxidation combining with absorption. The system comprises a gas-like phase reagent generating device, a preoxidation device and an absorption tower. The removal method comprises the following steps that 1, a gas-like phase composite oxidant is prepared; 2, a preoxidation reaction is performed, wherein the gas-like phase composite oxidant is utilized to efficiently oxidize NO and Hg<0> in a gas phase; 3, an absorption reaction is performed, wherein mixed liquor of sodium humate and ammonia water serves as absorption seriflux to absorb and remove SOx, NOx and Hg<2+> in oxidation products. According to the flue gas integration removal system and method by means of gas-like phase preoxidation combining with absorption, the two-level arrangement mode of combining preoxidation with absorption is adopted to perform integration removal on multiple pollutants of coal-fired flue gas, and therefore the problems that in an existing hierarchical arrangement mode, a system is complex, the floor space is large, and the operating cost is slightly high are solved; the desulfuration, denitration and mercury removal efficiency can meet the current pollutant discharge standard, a removal product is sulphureous and nitrogenous compound fertilizer, and higher economic and environmental benefits are achieved.

Description

Gas-like phase pre-oxidation combines the flue gas integration absorbed and removes system and method
Technical field
The invention belongs to flue gases purification field, the flue gas integration being specifically related to gas-like phase pre-oxidation combination absorption removes system and method.
Background technology
Coal fire discharged particle, SO 2, NO xwith trace heavy metal (Hg 0) be one of inducement causing China's haze to take place frequently, it brings serious threat to the life and health of the mankind and ecological sustainable development, therefore, extremely urgent to the control of coal-fired flue-gas pollutant.The existing desulfurization denitration demercuration system of thermal power plant is respectively Wet Limestone-gypsum system (WFGD), selective catalytic reduction system operating (SCR) and active carbon injected system (ACI), these processing modes are classification tandem, have that floor space is large, system complex and a higher defect of operating cost.Therefore, research and development have that equipment investment is few, operating cost is low and the new technology to flue gas and desulfurizing and denitrifying demercuration of non-secondary pollution has become the important directions in domestic and international coal-fired flue-gas Pollutant Control Technology field.
Have absorption process, absorption method, oxidizing process three kinds of technology at present for desulfurization denitration demercuration, wherein oxidizing process has more advantage in denitration demercuration.As everyone knows, in power production process, the NO of 90-95% in coal-fired flue-gas xbe NO, its poorly water-soluble cannot be absorbed by absorbent, causes denitration efficiency lower, and NO 2, NO 3and N 2o 5stronger etc. water-soluble; 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, Hg 0to remove be crucial, therefore, by Hg 0in gas phase, Quick Oxidation is Hg 2+it is the emphasis realizing demercuration.To sum up, oxidizing process is more conducive to SO in coal-fired flue-gas 2, NO and Hg 0integration remove.
Coal-fired flue-gas multi-pollutant purification techniques is mainly divided into Wet technique and dry technique.Wet technique is mainly divided into wet oxidation process and wet type Absorption via Chemical Complexation, and Wet technique has the advantage that removal efficiency is high, coal adaptability is strong and stable, but also there is the relatively high problem of chloride ion corrosion, wastewater treatment, energy consumption and operating cost.Dry technique has without advantages such as wastewater treatments, but has that system run all right is poor, removal efficiency is on the low side, cannot meet the shortcomings such as existing discharge standard.
Summary of the invention
For the deficiencies in the prior art, the flue gas integration that the invention provides gas-like phase pre-oxidation combination absorption removes system and method.
The technical solution used in the present invention is:
Gas-like phase pre-oxidation combines the flue gas integration absorbed and removes system, comprises gas-like phase reagent generating means, pre-oxidation device and wet absorption tower successively by technological process;
Described gas-like phase reagent generating means comprises fresh water (FW) import 1, condenser 2, high-temperature steam outlet 5 and blender 8;
Described pre-oxidation device is placed in the downstream of gas-like phase reagent generating means, and comprise the exhanst gas outlet 12 after gas-like phase composite oxidant entrance 10, smoke inlet 11 and flue gas and gas-like phase composite oxidant 9 mixed oxidization, described exhanst gas outlet 12 connects wet absorption tower;
Described wet absorption tower is placed in the downstream of pre-oxidation device, for absorbing slurries to the SO in oxidation product x, NO xand Hg 2+carry out absorbing and removing.
Further, described pre-oxidation device is cyclone type pre-oxidation device or inverted U pre-oxidation device.
Further, in condenser 2, be provided with fresh water (FW) generating tube 4, fresh water (FW) is vaporized wherein, and the high-temperature steam obtained enters blender 8 by high-temperature steam outlet 5.
Further, described condenser 2 is also provided with the entrance of heat smoke 3 after economizer, makes the fresh water (FW) in fresh water (FW) generating tube 4 carry out heating power vaporization.
Further, described blender 8 comprises the inlet port of liquid phase composite oxidant mother liquor 6 under the impact of compressed air 7 is carried; Also comprise the outlet of liquid phase composite oxidant mother liquor 6 and high-temperature steam process abundant mixing generation gas-like phase composite oxidant 9.
Upper described system carries out the method that flue gas integration removes, and comprises the following steps:
A. fresh water (FW) enters condenser 2 by fresh water (FW) import 1, vaporizes, obtain high-temperature steam in the fresh water (FW) generating tube 4 of fresh water (FW) in condenser 2; High-temperature steam enters blender 8 by high-temperature steam outlet 5;
B. liquid phase composite oxidant mother liquor 6 enters blender 8 under the impact of compressed air 7 is carried; In blender 8, vaporific liquid phase composite oxidant mother liquor 6 and high-temperature steam, through fully mixing, generate gas-like phase composite oxidant 9;
C. gas-like phase composite oxidant 9 enters pre-oxidation device by gas-like phase composite oxidant entrance 10, and former flue gas enters pre-oxidation device by smoke inlet 11 and mixes with gas-like phase composite oxidant 9, oxidation reaction occurs, realizes NO and Hg 0oxidation;
D. oxidation product discharges pre-oxidation device by exhanst gas outlet 12, enters wet absorption tower, with absorption slurries to the SO in oxidation product x, NO xand Hg 2+carry out absorbing and removing.
Preferably, described liquid phase composite oxidant is made up of oxidant and additive.
Preferably, described oxidant is one or more in hydrogen peroxide, sodium peroxydisulfate and sodium chlorite; Described additive is one or more in sodium bromide, nickel nitrate and glacial acetic acid; In described oxidant, the concentration of hydrogen peroxide is 15-30%wt, and sodium peroxydisulfate concentration is 1-10%wt, and sodium chlorite concentrations is 0.5-10%wt, and in described additive, the concentration of sodium bromide, nickel nitrate, glacial acetic acid is 0.1-2%wt.
Preferably, the temperature of described gas-like phase reagent generating means is 130-170 DEG C.
Preferably, the former gas residence time in described pre-oxidation reactor is 1-3s.
Preferably, the gas liquid ratio of described former flue gas and liquid phase composite oxidant is 10 4m 3: (13-40) L is 1m with the gas liquid ratio of absorption slurries 3: (5-10) L.
Preferably, described absorption slurries are the mixed liquor of sodium humate and ammoniacal liquor, and pH is 9-12; Described sodium humate concentration is 0.1-1.0%wt, and described ammonia concn is 10-20%wt.
Preferred liquid phase composite oxidant combining form comprises:
(1) hydrogen peroxide/sodium chlorite: the two concentration ratio is 25-30%wt:0.5-1%wt, pH scope is 4-6;
(2) sodium chlorite/sodium peroxydisulfate: the two concentration ratio is 2-4%wt:1-5%wt, pH scope is 10-12;
(3) sodium chlorite/sodium bromide: the two concentration ratio is 4-10%wt:0.1-0.3%wt, pH scope is 6-11;
(4) hydrogen peroxide/glacial acetic acid/sodium bromide: three's concentration ratio is 15-25%wt:1-2%wt:1-1.5%wt, pH scope is 1-3;
(5) sodium peroxydisulfate/sodium bromide/nickel nitrate: three's concentration ratio is 8-10%wt:0.1-0.3%wt:0.1-0.5%wt, pH scope is 7-10.
Described liquid phase composite oxidant mother liquor preparation process is: after oxidant and additive being mixed in proportion, utilize fresh water (FW) to be diluted to mother liquid concentration.Above-mentioned multiple composite oxidant has stronger stability, without significant a large amount of air release phenomenon in 12h, is conducive to the safe operation of the preparation of liquid phase composite oxidant and stocking system thereof.
Described pre-oxidation device is cyclone type pre-oxidation device or inverted U pre-oxidation device.Cyclone type pre-oxidation device runs as follows: gas-like phase composite oxidant 9 and former flue gas carry out moving to die-cut stream, top-down rotary motion is carried out in the bucket wall side of cyclone type pre-oxidation device, in the process, gas-like phase composite oxidant 9 and former flue gas carry out turbulent closure scheme and oxidation reaction occur, in sleeve, rotary motion is from bottom to top carried out, until discharge pre-oxidation reactor after former flue gas touches the end.
Inverted U pre-oxidation device runs as follows: former flue gas accelerates in the Venturi tube of inverted U pre-oxidation device, gas-like phase composite oxidant 9 sprays in Venturi tube reducing place, and the former smoke-shock after acceleration also carries gas-like phase composite oxidant and enters pre-oxidation device main part; Perforated baffle is arranged in Venturi exit place to strengthen the turbulating effect of flue gas, improves the decentralization of pollutant in oxidant and flue gas, accelerates oxidation efficiency; Mixed former flue gas carries out flowing and oxidation reaction occurring in inverted U pre-oxidation device inside, until discharge pre-oxidation reactor.
The operating condition condition of gas-like phase reagent generating means, pre-oxidation device and wet scrubbing tower is as follows:
(1) the heat smoke temperature of gas-like phase reagent generating means is 130-170 DEG C;
(2), in gas-like phase reagent generating means, the gas liquid ratio of former flue gas and liquid phase composite oxidant is 10 4m 3: (13-40) L (operating mode exhaust gas volumn);
(3) the range of reaction temperature 70-120 DEG C in pre-oxidation device;
(4) the former gas residence time in pre-oxidation device is 1-3s;
(5) the absorption slurries in wet scrubbing tower are the mixed liquor of sodium humate and ammoniacal liquor, and pH is 9-12; Sodium humate concentration is 0.1-1.0%wt, and ammonia concn is 10-20%wt;
(6) the pH scope of sodium humate and ammonia water mixture is 9-12;
(7) former flue gas is 1m with the gas liquid ratio of absorption slurries 3: (5-10) L.
Above-mentioned gas-like phase pre-oxidation combines the optimum desulfurization denitration demercuration efficiency absorbing coal-fired flue-gas multi-pollutant integration removing sulfuldioxide can reach 99-100%, 88-92% and 90-95% respectively.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 of the oxidation-absorption secondary treatment system of this integrated form are lower, operate more easy, remove product and be conducive to recycling, therefore have good economy and environment benefit.
Technical process of the present invention is a kind of two stage treatment technology---gas-like phase pre-oxidation is in conjunction with absorption techniques, and namely by utilizing coal steam-electric plant smoke waste heat to vaporize liquid phase composite oxidant, the gas-like phase composite oxidant then generated realizes NO and Hg in pre-oxidation device 0quick Oxidation, oxidation product and residual gas-like phase composite oxidant are absorbed by follow-up sodium humate/ammonia absorption liquid.The present invention is applicable to polytype boiler, and can realize removing to multiple flue gas pollutant simultaneously, and therefore this invention has good environmental benefit and economic benefit, has broad application prospects.
Reaction mechanism of the present invention is as follows:
Hydrogen peroxide, over cure acid group, sodium chlorite are the once oxidation agent of this liquid phase composite oxidant, peroxide root, potentiometric titrations, hydroxyl radical free radical, chlorine dioxide, chlorine radical, Peracetic acid, bromine simple substance, bromine free radical etc. are secondary oxidation agent, and these oxidants are by NO, the Hg in flue gas 0be oxidized to bivalent mercury, NO is oxidized to NO x.Synergistic Mechanisms between oxidant is as follows:
H 2O 2+NaClO 2→HO 2 -+HClO 2→ClO 2+M→Cl ·+Cl 2
H 2O+Na 2S 2O 8+H 2O 2→SO 4 ·-+HO ·→HSO 5 -
H 2O+Na 2S 2O 8+NaClO 2→SO 4 ·-+ClO 2+M→HSO 5 -+Cl ·+Cl 2
Between oxidant and additive, Synergistic Mechanisms is as follows:
H 2O 2+CH 3COOH→CH 3COOOH
Ni 3++Na 2S 2O 8+H 2O→SO 4 ·-+HO ·→HSO 5 -
Br -+ oxidant/free radical → Br -+ Br 2
Reaction mechanism is as follows once and between secondary oxidation agent and pollutant:
H 2O 2+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+H 2O
Na 2S 2O 8+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+SO 4 2-
NaClO 2+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+Cl -
ClO 2+Cl ·+Cl 2+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+Cl -
SO 4 ·-+HO ·+HSO 5 -+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)
SO 4 ·-+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+SO 4 2-
CH 3COOOH+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+CH 3COOH
Br ·-+Br 2+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)+Br -
H 2O 2+N(II)+Hg 0+S(IV)→N(V)+Hg(II)+S(VI)
Between oxidation product and absorbent, reaction mechanism is as follows:
H 2O+NH 3+N(V)+S(VI)→(NH 4) 2SO 4+NH 4NO 3
A -(humic acid group)+NO 2→ HA+NO 3 -
A -+SO 3+SO 2→HA+SO 3 2-+SO 4 2-
Adopt multiple composite oxidant of the present invention to carry out desulfurization denitration demercuration process to flue gas, treatment effect is as shown in table 1:
Table 1 desulfurization denitration demercuration effect
Project Before process After process Removal efficiency
Hg 0Concentration 30μg/m 3 1.5-3μg/m 3 90-95%
NO concentration 500mg/m 3 40-60mg/m 3 88-92%
SO 2Concentration 4000mg/m 3 0-40mg/m 3 99-100%
Beneficial effect of the present invention is:
1, the inventive method is unique, utilizes gas-like phase composite oxidant first to NO and Hg in flue gas 0be oxidized, then realize SO 2, NO and Hg 0remove simultaneously, thus realize desulfurization denitration demercuration integration, greatly reduce capital construction and the operating cost of grading desulfurization denitration demercuration, improve integrated removal efficiency, the product that removes obtained is the nitrogenous composite fertilizer of a kind of excellent sulfur-bearing, has higher economy and environment benefit.
2, the present invention efficiently utilizes heat smoke waste heat, improves the thermal efficiency.
3, gas-like phase pre-oxidation combines the technology absorbed and is applicable to multiple Industrial Boiler, is one of feasible scheme solving northern coal smoke type haze.
Accompanying drawing explanation
Fig. 1 is that gas-like phase pre-oxidation of the present invention combines absorption coal-fired flue-gas multi-pollutant integration removing process schematic flow sheet.
Fig. 2 is gas-like phase reagent generating means schematic diagram.
Fig. 3 is cyclone type pre-oxidation apparatus schematic diagram.
Fig. 4 is inverted U pre-oxidation apparatus schematic diagram.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed.
Gas-like phase pre-oxidation combines the flue gas integration absorbed and removes system, comprises gas-like phase reagent generating means, pre-oxidation device and wet absorption tower; Its structure respectively as shown in Figure 2,3, 4.In figure, the concrete meaning of each label is as follows: the import of 1-fresh water (FW), 2-condenser, heat smoke after 3-economizer, 4-fresh water (FW) generating tube, 5-high-temperature steam outlet, 6-liquid phase composite oxidant mother liquor, 7-compressed air, 8-blender, 9-gas-like phase composite oxidant, 10-gas-like phase composite oxidant entrance, 11-smoke inlet, 12-exhanst gas outlet, 13-hydroecium, 14-housing, 15-gripper shoe, flue gas after 16-cooling, 17-shell, the left-handed unit sheet of 18-, 19-dextrorotation unit sheet.
Described gas-like phase reagent generating means comprises fresh water (FW) import 1, condenser 2, high-temperature steam outlet 5 and blender 8;
Described pre-oxidation device is placed in the downstream of gas-like phase reagent generating means, comprises gas-like phase composite oxidant entrance 10, smoke inlet 11 and exhanst gas outlet 12.
Described pre-oxidation device is cyclone type pre-oxidation device or inverted U pre-oxidation device.
Fresh water (FW) enters condenser 2 by fresh water (FW) import 1, vaporizes, obtain high-temperature steam in the fresh water (FW) generating tube 4 in condenser 2; High-temperature steam enters blender 8 by high-temperature steam outlet 5;
Liquid phase composite oxidant mother liquor 6 enters blender 8 under the impact of compressed air 7 is carried; In blender 8, vaporific liquid phase composite oxidant mother liquor 6 and high-temperature steam, through fully mixing, generate gas-like phase composite oxidant 9;
Gas-like phase composite oxidant 9 enters pre-oxidation device by gas-like phase composite oxidant entrance 10, and former flue gas enters pre-oxidation device by smoke inlet 11 and mixes with gas-like phase composite oxidant 9, oxidation reaction occurs, realizes NO and Hg 0oxidation;
Oxidation product discharges pre-oxidation device by exhanst gas outlet 12, enters wet absorption tower, with absorption slurries to the SO in oxidation product x, NO xand Hg 2+carry out absorbing and removing.
Fresh water (FW) after described condenser 2 uses economizer in heat smoke 3 pairs of fresh water (FW) generating tubes 4 carries out heating power vaporization.
Described liquid phase composite oxidant is made up of oxidant and additive.
Described oxidant is one or more in hydrogen peroxide, sodium peroxydisulfate and sodium chlorite; Described additive is one or more in sodium bromide, nickel nitrate and glacial acetic acid; In described oxidant, the concentration of hydrogen peroxide is 15-30%wt, and sodium peroxydisulfate concentration is 1-10%wt, and sodium chlorite concentrations is 0.5-10%wt, and in described additive, the concentration of sodium bromide, nickel nitrate, glacial acetic acid is 0.1-2%wt.
Embodiment 1
Preparation liquid phase composite oxidant mother liquor: wherein the concentration %wt of hydrogen peroxide and sodium chlorite is than being 25:1, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 4.5.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 2.
Table 2 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 130℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 13L:10 4m 3
Reaction temperature in pre-oxidation device 70℃
Gas residence time in pre-oxidation device 1.3s
Sodium humate and ammonia concn ratio 0.1:10%wt
The pH of sodium humate and ammonia water mixture 9
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 99%, denitration efficiency is 90.5%, and demercuration efficiency is more than 92.7%.
Embodiment 2
Preparation composite oxidant: wherein the concentration %wt of hydrogen peroxide and sodium chlorite is than being 30:0.5, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 5.7.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 3.
Table 3 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 150℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 30L:10 4m 3
Reaction temperature in pre-oxidation device 100℃
Gas residence time in pre-oxidation device 1.0s
Sodium humate and ammonia concn ratio 0.5:15%wt
The pH of sodium humate and ammonia water mixture 10
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 89.2%, and demercuration efficiency is more than 93.3%.
Embodiment 3
Preparation composite oxidant: wherein the concentration %wt of sodium chlorite and sodium peroxydisulfate is than being 2:4, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 10.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 4.
Table 4 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 140℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 20L:10 4m 3
Reaction temperature in pre-oxidation device 120℃
Gas residence time in pre-oxidation device 1.0s
Sodium humate and ammonia concn ratio 1.0:15%wt
The pH of sodium humate and ammonia water mixture 10.5
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 92.0%, and demercuration efficiency is more than 94.8%.
Embodiment 4
Preparation composite oxidant: wherein the concentration %wt of sodium chlorite and sodium peroxydisulfate is than being 4:4, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 11.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 5.
Table 5 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 170℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 25L:10 4m 3
Reaction temperature in pre-oxidation device 100℃
Gas residence time in pre-oxidation device 2.4s
Sodium humate and ammonia concn ratio 0.5:20%wt
The pH of sodium humate and ammonia water mixture 12
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 92.0%, and demercuration efficiency is more than 95.0%.
Embodiment 5
Preparation composite oxidant: wherein the concentration %wt of sodium chlorite and sodium bromide is than being 4:0.1, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 8.5.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 6.
Table 6 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 160℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 20L:10 4m 3
Reaction temperature in pre-oxidation device 130℃
Gas residence time in pre-oxidation device 2.7s
Sodium humate and ammonia concn ratio 0.3:20%wt
The pH of sodium humate and ammonia water mixture 10.5
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 99.3%, denitration efficiency is 88.4%, and demercuration efficiency is more than 94.3%.
Embodiment 6
Preparation composite oxidant: wherein the concentration %wt of sodium chlorite and sodium bromide is than being 10:0.3, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 11.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 7.
Table 7 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 170℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 13L:10 4m 3
Reaction temperature in pre-oxidation device 120℃
Gas residence time in pre-oxidation device 1s
Sodium humate and ammonia concn ratio 1:20%wt
The pH of sodium humate and ammonia water mixture 12
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 91.8%, and demercuration efficiency is more than 95.0%.
Embodiment 7
Preparation composite oxidant: wherein the concentration %wt of hydrogen peroxide, glacial acetic acid and sodium bromide is than being 15:2:1.5, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 2.5.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 8.
Table 8 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 130℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 40L:10 4m 3
Reaction temperature in pre-oxidation device 80℃
Gas residence time in pre-oxidation device 3s
Sodium humate and ammonia concn ratio 0.5:20%wt
The pH of sodium humate and ammonia water mixture 12
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 91.4%, and demercuration efficiency is more than 93.2%.
Embodiment 8
Preparation composite oxidant: wherein the concentration %wt of hydrogen peroxide, glacial acetic acid and sodium bromide is than being 25:1:1, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 1.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 9.
Table 9 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 130℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 35L:10 4m 3
Reaction temperature in pre-oxidation device 110℃
Gas residence time in pre-oxidation device 2s
Sodium humate and ammonia concn ratio 0.3:20%wt
The pH of sodium humate and ammonia water mixture 9
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 99%, denitration efficiency is 90.2%, and demercuration efficiency is more than 91.4%.
Embodiment 9
Preparation composite oxidant: wherein the concentration %wt of sodium peroxydisulfate, sodium bromide and nickel nitrate is than being 8:0.1:0.1, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 7.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 10.
Table 10 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 150℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 30L:10 4m 3
Reaction temperature in pre-oxidation device 120℃
Gas residence time in pre-oxidation device 2.7s
Sodium humate and ammonia concn ratio 1:20%wt
The pH of sodium humate and ammonia water mixture 10
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 88.9%, and demercuration efficiency is more than 89.5%.
Embodiment 10
Preparation composite oxidant: wherein the concentration %wt of sodium peroxydisulfate, sodium bromide and nickel nitrate is than being 10:0.3:0.5, and by both by after above-mentioned concentration ratio mixing, utilize fresh water (FW) to be diluted to mother liquid concentration, pH is 10.
Above-mentioned liquid phase composite oxidant is injected gas-like phase reagent generating means, after pre-oxidation device, wet absorption tower, realize integration desulfurization denitration demercuration, reaction condition is in table 11.
Table 11 reaction condition
Condition Scope
Temperature in gas-like phase composite oxidant generating means 140℃
The liquid-gas ratio of liquid phase composite oxidant addition and exhaust gas volumn 25L:10 4m 3
Reaction temperature in pre-oxidation device 100℃
Gas residence time in pre-oxidation device 2s
Sodium humate and ammonia concn ratio 0.8:10%wt
The pH of sodium humate and ammonia water mixture 10
Carry out desulfuration demercuration denitration process by above-mentioned condition to flue gas, detection obtains: SO 2removal efficiency be 100%, denitration efficiency is 89.4%, and demercuration efficiency is more than 91.2%.
The present invention is not departing under its spirit and substantive characteristics prerequisite, multiple detailed description of the invention can be had, be to be understood that above-described embodiment is not limited to above-mentioned any details, and should be widely interpreted in the spirit and scope that claims define, therefore, all drop on claim border and scope in or with the change of these borders and scope equivalence with revise and all attempt to be included in accessory claim.

Claims (10)

1. gas-like phase pre-oxidation combines the flue gas integration absorbed and removes system, it is characterized in that, comprises gas-like phase reagent generating means, pre-oxidation device and wet absorption tower successively by flow process;
Described gas-like phase reagent generating means comprises fresh water (FW) import (1), condenser (2), high-temperature steam outlet (5) and blender (8);
Described pre-oxidation device is placed in the downstream of gas-like phase reagent generating means, comprise the exhanst gas outlet (12) after gas-like phase composite oxidant entrance (10), smoke inlet (11) and flue gas and gas-like phase composite oxidant (9) mixed oxidization, described exhanst gas outlet (12) connects wet absorption tower;
Described wet absorption tower is placed in the downstream of pre-oxidation device, for absorbing slurries to the SO in oxidation product x, NO xand Hg 2+carry out absorbing and removing.
2. according to claim 1ly remove system, it is characterized in that, described pre-oxidation device is cyclone type pre-oxidation device or inverted U pre-oxidation device.
3. according to claim 1ly remove system, it is characterized in that, fresh water (FW) generating tube (4) is provided with in condenser (2), fresh water (FW) is vaporized wherein, and the high-temperature steam obtained enters blender (8) by high-temperature steam outlet (5).
4. according to claim 1ly remove system, it is characterized in that, described condenser (2) is also provided with the entrance of heat smoke (3) after economizer, makes the fresh water (FW) in fresh water (FW) generating tube (4) carry out heating power vaporization.
5. according to claim 1ly remove system, it is characterized in that, described blender (8) comprises the inlet port of liquid phase composite oxidant mother liquor (6) under the impact of compressed air (7) is carried; Also comprise the outlet of liquid phase composite oxidant mother liquor (6) and abundant mixing generation gas-like phase composite oxidant (9) of high-temperature steam process.
6. system according to claim 1 carries out the method that flue gas integration removes, and it is characterized in that, comprises the following steps:
A. fresh water (FW) enters condenser (2) by fresh water (FW) import (1), in the fresh water (FW) generating tube (4) in condenser (2), vapour occurs
Change, obtain high-temperature steam; High-temperature steam enters blender (8) by high-temperature steam outlet (5);
B. liquid phase composite oxidant mother liquor (6) enters blender (8) under the impact of compressed air (7) is carried; In blender (8), vaporific liquid phase composite oxidant mother liquor (6) and high-temperature steam, through fully mixing, generate gas-like phase composite oxidant (9);
C. gas-like phase composite oxidant (9) enters pre-oxidation device by gas-like phase composite oxidant entrance (10), former flue gas enters pre-oxidation device by smoke inlet (11) and mixes with gas-like phase composite oxidant (9), there is oxidation reaction, realize NO and Hg 0oxidation;
D. oxidation product discharges pre-oxidation device by exhanst gas outlet (12), enters wet absorption tower, with absorption slurries to the SO in oxidation product x, NO xand Hg 2+carry out absorbing and removing.
7. method according to claim 6, is characterized in that, described liquid phase composite oxidant is made up of oxidant and additive.
8. method according to claim 7, is characterized in that, described oxidant is one or more in hydrogen peroxide, sodium peroxydisulfate and sodium chlorite; Described additive is one or more in sodium bromide, nickel nitrate and glacial acetic acid; In described oxidant, the concentration of hydrogen peroxide is 15-30%wt, and sodium peroxydisulfate concentration is 1-10%wt, and sodium chlorite concentrations is 0.5-10%wt, and in described additive, the concentration of sodium bromide, nickel nitrate, glacial acetic acid is 0.1-2%wt.
9. method according to claim 6, is characterized in that, the temperature of described gas-like phase reagent generating means is 130-170 DEG C; Former gas residence time in described pre-oxidation reactor is 1-3s; The gas liquid ratio of described former flue gas and liquid phase composite oxidant is 10 4m 3: (13-40) L is 1m with the gas liquid ratio of absorption slurries 3: (5-10) L.
10. method according to claim 6, is characterized in that, described absorption slurries are the mixed liquor of sodium humate and ammoniacal liquor, and pH is 9-12; Described sodium humate concentration is 0.1-1.0%wt, and described ammonia concn is 10-20%wt.
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CN105289236A (en) * 2015-11-23 2016-02-03 中南大学 Synchronous desulfurization and denitrification process for reinforcing sintered flue gas based on NO oxidization by hydrogen peroxide and potassium permanganate
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CN105879678A (en) * 2016-05-23 2016-08-24 大连海事大学 Comprehensive treatment method and device of waste gas of ship on basis of seawater electrolysis
CN106178909A (en) * 2016-09-14 2016-12-07 湖南省小尹无忌环境能源科技开发有限公司 Preparation oxidation soil release agent is for removing heavy metal in flue gas and the system of fluorine chlorine sulfur nitre
CN106178909B (en) * 2016-09-14 2018-10-26 湖南省小尹无忌环境能源科技开发有限公司 Prepare the system that oxidation soil release agent is used to remove heavy metal in flue gas and fluorine chlorine sulphur nitre
CN108754179A (en) * 2018-06-13 2018-11-06 中南大学 A kind of method of oxidation pre-treatment secondary material containing zinc
CN109865415A (en) * 2019-04-08 2019-06-11 福建省特种设备检验研究院 CFB boiler, which is mixed, burns anthracite and sawdust sludge gas mercury oxidation control technique
CN110332558A (en) * 2019-08-20 2019-10-15 华中科技大学 A kind of supercharged oxygen-enriched flue gas desulfurization and denitrification demercuration system

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