CN110787617A - Sintering flue gas semi-dry desulfurization and denitrification integrated device and method - Google Patents
Sintering flue gas semi-dry desulfurization and denitrification integrated device and method Download PDFInfo
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- 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
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- B01D2258/0283—Flue gases
Abstract
The invention discloses a sintering flue gas semi-dry desulfurization and denitrification integrated device and method, and belongs to the technical field of desulfurization and denitrification. The device comprises a sintering machine, an electric dust collector, a main exhaust fan, an oxidant tank, a rotary atomizer, a SDA (first order draft) desulfurization tower, a reducing agent absorption tank, a supplementary absorbent tank, a bag-type dust collector, a booster fan and a flue gas monitoring device; the method comprises the steps of firstly, dedusting flue gas by an electric precipitator, then feeding the flue gas into a flue, spraying a denitration oxidant component A into the flue, feeding the treated flue gas into an SDA (serial data architecture) desulfurization tower, spraying the flue gas by slaked lime slurry, and spraying a denitration reduction absorbent component B into the SDA desulfurization tower by a high-pressure spray gun; and spraying the denitration supplementary absorbent component C into a pipeline between an exhaust outlet of the SDA desulfurization tower and the bag-type dust remover, and discharging the purified flue gas through a chimney after the dust of the bag-type dust remover is removed. The method is simple, low in operation cost and obvious in environment-friendly benefit.
Description
The technical field is as follows:
the invention belongs to the technical field of desulfurization and denitrification, and particularly relates to a sintering flue gas semi-dry desulfurization and denitrification integrated device and method.
Background art:
in iron and steel enterprises in China, sintering is an essential process in the production flow, and occupies more than 70 percent of the supply of iron-containing raw materials in a blast furnace. But the process also has the largest pollutant discharge amount of iron and steel enterprises, wherein SO2、NOXThe equal discharge amount respectively accounts for about 70 percent and 50 percent of the total discharge amount of the iron and steel enterprises. With the stricter environmental protection policy, China redacted the emission standard of atmospheric pollutants for the steel sintering and pellet industry (GB28662-2012) in 2012, wherein the emission indexes of various pollutants have stricter requirements. At present, domestic flue gas desulfurization technology and equipment are relatively perfect, but more than 99% of sintering machines before 2014 do not have a single denitration device, and if the construction of a denitration project is added to meet the requirement of nitrogen oxide emission, a large amount of capital is certainly spent, which is obviously impossible for the current situation of enterprises, so that the provision of an economic and efficient integrated technical scheme for desulfurization and denitration becomes the most urgent need of the current steel industry.
Chinese patent CN103990375A discloses an integrated purification method for sintering flue gas by a semi-dry method, which can carry out high-efficiency desulfurization, denitration and dioxin and heavy metal removal on the sintering flue gas, an oxidant generation and distribution device is inserted in a flue gas pipeline in front of an absorption reaction tower of a semi-dry desulfurization system, and the evenly sprayed oxidant fully reacts with NO in the flue gas to oxidize the NO in the flue gas into NO2Then enters an absorption reaction tower to react with an absorbent,can achieve the aims of desulfurization, denitration and dioxin and heavy metal removal. However, as the operation time of the process is longer, a large amount of nitrate and nitrite are generated in the later period and are difficult to treat, wherein the nitrite belongs to dangerous waste and can cause great influence on the environment.
In order to solve the problems, the invention provides a method for achieving the effect of oxidation-reduction absorption by adding auxiliary devices and applying denitration catalyst components without changing the original process, and the finally obtained by-product is mainly CaSO4·H2O and Ca (NO)3)2Etc., can produce higher added values.
The invention content is as follows:
the invention aims to provide a sintering flue gas semi-dry desulfurization and denitrification integrated device and method which are low in operation cost and high in desulfurization and denitrification efficiency, and further integration of desulfurization and denitrification can be realized.
The invention provides a sintering flue gas semi-dry desulfurization and denitrification integrated device which comprises a sintering machine 1, an inlet flue gas monitoring device, an electric dust remover, a main exhaust fan, an oxidant tank 5, a rotary atomizer 6, a top tank 7, a SDA (rotating spray drying) desulfurization tower 8, a reducing agent absorption tank 9, a supplementary absorbent tank 10, a bag-type dust remover 11, a booster fan 12, an outlet flue gas monitoring device 13 and a chimney 14; the sintering machine 1, the inlet flue gas monitoring device, the electric dust remover, the main exhaust fan, the rotary atomizer 6, the SDA desulfurization tower 8, the supplementary absorbent tank 10, the bag-type dust remover 11, the booster fan 12, the outlet flue gas monitoring device 13 and the chimney 14 are connected in sequence.
Import flue gas monitoring devices includes first import flue gas monitoring devices 2A and second import flue gas monitoring devices 2B, the electrostatic precipitator includes first electrostatic precipitator 3A and second electrostatic precipitator 3B, main air exhauster includes the main air exhauster 4B of first main air exhauster 4A and second.
The inlet flue gas monitoring device, the electric dust remover and the main exhaust fan are respectively provided with two devices which are connected in parallel, one device is used for standby, the first main exhaust fan 4A and the second main exhaust fan 4B are respectively connected with the oxidant tank 5 through two high-pressure spray guns, the number of the spray guns is four, the two devices are used for standby, and the distance between the front part and the rear part of each two spray guns is 2-5 m; the rotary atomizer 6 is connected with the upper part of the SDA desulfurization tower 8; two high-pressure spray guns are arranged in the SDA desulfurization tower 8, one is used for the other, and the two high-pressure spray guns in the SDA desulfurization tower 8 are both connected with the reduction absorbent tank 9.
The denitration catalyst comprises an oxidant tank 5, a reduction absorbent tank 9, a denitration reduction absorbent tank 9 and a supplementary absorbent tank 10, wherein the oxidant tank 5 is filled with a denitration oxidant component A, the reduction absorbent tank 9 is filled with a denitration reduction absorbent component B, and the supplementary absorbent tank 10 is filled with a denitration supplementary absorbent component C, wherein the denitration supplementary absorbent component C is used as a supplement according to the redox absorption conditions of the denitration oxidant component A and the denitration reduction absorbent component B.
The invention also provides a desulfurization and denitrification integrated method of the sintering flue gas semi-dry desulfurization and denitrification integrated device, which comprises the following specific steps:
(1) the flue gas from the sintering machine equipment is dedusted by an electric deduster to greatly reduce the amount of the flue gas, and the flue gas is subjected to air draft by a main exhaust fan and enters a flue;
(2) simultaneously, the denitration oxidant component A is sprayed into a flue on the right side of the main exhaust fan through a high-pressure spray gun, part of NO in the flue gas is quickly oxidized into high-valence nitrogen oxide by the denitration oxidant component A, and part of SO2Is also oxidized to SO3；
Wherein, the oxidation reaction in the pipeline in which the denitration oxidant component A is sprayed is as follows:
NO+NO2→N2O3
(3) the oxidized smoke enters the flue gasIn the SDA desulfurization tower 8, slaked lime slurry is simultaneously atomized into fine fog drops (average less than 50 mu m) through the rotary atomizer 6 to spray flue gas, and meanwhile, a denitration reduction absorbent component B is sprayed into the SDA desulfurization tower 8 through a high-pressure spray gun; in the SDA desulfurization tower 8, the flue gas, the serous fluid and the denitration reduction absorbent component B are fully mixed, contacted and reacted, and the unreacted SO in the first step of the flue gas is2Other acidic substances are absorbed and neutralized, part of high-valence nitrogen oxides are reduced into stable zero-valence nitrogen, and meanwhile, water is evaporated to quickly finish atomization, absorption and drying; the dry dust-containing gas enters the outlet pipeline of the SDA desulfurization tower 8 to be discharged, and the generated CaSO4·H2O、Ca(NO3)2And a small amount of CaSO3·1/2H2O、CaCl2、CaCO3And Ca (OH)2The byproducts are output through an outward pipeline and can be used as a cement coagulation regulator to play a role in retarding coagulation;
wherein, the desulfurization and denitrification reaction in the SDA desulfurization tower is as follows:
SO2+Ca(OH)2→CaSO3+H2O
SO3+Ca(OH)2→CaSO4+H2O
NO2+H2O→HNO3+NO
N2O3+H2O→2HNO2
N2O5+H2O→2HNO3
2HCl+Ca(OH)2→CaCl2+2H2O
HNO3+Ca(OH)2→Ca(NO3)2+H2O
2HNO2+Ca(OH)2→Ca(NO2)2+2H2O
2HNO2+CO(NH2)2→2N2+CO2+3H2O
Ca(NO2)2+SO3+O2→CaSO4+NO2
(4) spraying the denitration supplement absorbent component C into a pipeline between the exhaust outlet of the SDA desulfurization tower 8 and the bag-type dust remover 11 through a high-pressure spray gun to be used as a supplement scheme after SDA desulfurization and denitration SO as to ensure SO2And NOXRelatively ultra-clean emissions. The purified flue gas is dedusted by the bag-type dust collector 11 and then pressurized by the booster fan 12, and the flue gas is introduced into the chimney 14 to be discharged. The discharged material is mainly N2、CO2、H2O、O2And a small amount of CO and ash.
The denitration oxidant component A is an aqueous product prepared from 10-12 wt% of stable chlorine dioxide, 18-20 wt% of sodium chlorite in an alkaline system, 1-2 wt% of ferric sulfate and 1-2 wt% of sodium sulfate.
Concretely preparing SO according to different flue gases2、NOXContent of (2), control of NO/NO2The degree of oxidation of (A) is in the range of 0.5 to 0.9, and NO is selectedXPreparing water solution with the content of strong oxidant with equal molar ratio, adding Fe2(SO4)3As metal catalyst, sodium sulfate is used as cocatalyst.
The denitration reduction absorbent component B comprises 30-35 wt% of urea or paraformaldehyde and 0.6-1.8 wt% of FeSO4·7H2O, 0.3 to 0.7 wt% of Na2S2O3Or Na2SO3And 0.01 wt% of polyvinyl alcohol 200-400. The specific formulation is according to NO2/NOXDegree of oxidation of (2) and NO in flue gasXAnd SO2Content of (B), selecting NO in the flue gasXPreparing aqueous solution from 4-5 equivalent ratios of urea or paraformaldehyde, and adding FeSO4·7H2O is metal catalysisAgent, Na2S2O3Or Na2SO3An aqueous solution is prepared by an auxiliary catalytic reducing agent, 200-400 parts of polyvinyl alcohol is selectively added to increase the atomization effect, and the aqueous solution is atomized into an SDA desulfurization tower through a high-pressure spray gun of a denitration tank.
The denitration supplementary absorbent component C is an aqueous solution composed of 30-35 wt% of newly prepared urea and 1-2 wt% of a ferrous complex catalyst, wherein the ferrous complex catalyst is ethylenediaminetetraacetic acid ferrous iron (Fe) (EDTA), nitrilotriacetic acid ferrous iron (Fe (NTA), dimercaptopropane sulfate and a ferrous ion compound Fe (DMPS)2Any one or a mixture of two or more of them.
The invention has the following technical characteristics:
(1) the denitration process engineering is modified on the basis of not changing the original SDA desulfurization process, so that the integration of desulfurization and denitration is achieved.
(2) The integrated desulfurization and denitrification process is simple, low in resistance, simple and convenient to maintain, operate and operate, low in operation cost and capable of regulating and controlling the sintering flue gas desulfurization and denitrification slurry and the like at any time, so that the state of high removal efficiency is kept.
(3) The raw materials of the desulfurizer and the denitrifier are wide in source and low in price, and a solid oxidation catalyst is not used in the flue gas desulfurization and denitration process, so that the investment of equipment modification engineering and raw material cost is low.
(4) The denitrated product is N2、CO2、H2O、O2And a small amount of CO and ash slag, and no secondary pollutants are generated.
(5) The technology is provided with a supplementary scheme after SDA desulfurization and denitrification to ensure SO2And NOXAnd ultra-clean discharge is realized as far as possible.
(6) The reaction conditions in the desulfurization and denitrification processes are mild, and the components of the desulfurization and denitrification agent are all alkaline systems, so that the corrosion to equipment is small.
(7) The SDA process not only reduces the dosage of the slurry, but also greatly improves the desulfurization and denitrification efficiency.
(8) The slurry sprayed into the SDA desulfurization tower adopts Ca (OH)2The slurry can not cause the CaO powder in the dust collector to absorb water and release heat, so that the cloth bag of the cloth bag dust collector is burnt or ash conveying is blocked.
(9) The process has strong adaptability and adjustability to the working conditions of sintering flue gas under different conditions.
(10) The solid product after desulfurization and denitrification can be used as a coagulation regulator for cement production through analysis, and the high added value of the byproducts is improved.
Description of the drawings:
FIG. 1 is a schematic structural diagram of the integrated desulfurization and denitrification apparatus of the present invention.
In the figure: 1: sintering machine, 2A: first import flue gas monitoring devices, 2B: second import flue gas monitoring devices, 3A: first electrostatic precipitator, 3B: second electrostatic precipitator, 4A: first main draft fan, 4B: second main draft fan, 5: oxidant tank, 6: rotary atomizer, 7: top tank, 8: SDA desulfurization tower, 9: reducing absorbent tank, 10: make-up absorbent tank, 11: bag-type dust collector, 12: booster fan, 13: outlet flue gas monitoring device, 14: and (4) a chimney.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following specific embodiments. The following specific examples are all the most preferred examples.
Example 1: the flue gas amount of the sintering flue gas is 110 ten thousand Nm3H is used as the reference value. The flue gas from the sintering machine equipment is dedusted by an electric precipitator so as to greatly reduce the amount of the flue gas, and the flue gas is subjected to air draft by a main exhaust fan and enters a flue. Simultaneously, the denitration oxidant component A is sprayed into a flue on the right side of the main exhaust fan through a high-pressure spray gun, and part of NO in the flue gas is quickly oxidized into high-valence nitrogen oxide and SO by the denitration oxidant component A2Oxidation to SO3The amount of the denitration oxidant component A consumed is about 425-430 Kg/h. Then, the flue gas after oxidation treatment enters an SDA (first order absorption) desulfurization tower, meanwhile, slaked lime slurry is atomized into ultrafine fog drops (average size is less than 50 mu m) through a rotary atomizer to spray the flue gas, and at the moment, the denitration reduction absorbent component B also passes through a high-pressure spray gunSpraying into a SDA desulfurization tower; in the SDA desulfurization tower, the flue gas, the serous fluid and the denitration reduction absorbent component B are fully mixed, contacted and reacted, and the unreacted SO in the first step of the flue gas is2The acidic substances are absorbed and neutralized, and part of the high-valence nitrogen oxides are reduced into nitrogen (N)2) And simultaneously evaporating water to quickly finish atomization, absorption and drying, wherein the consumption of the denitration reduction absorbent component B is 991.8-1322.4 Kg/h. And (4) discharging the dried dust-containing gas into an outlet pipeline of the SDA desulfurization tower, and outputting the generated solid by-product through an outward transportation pipeline. Spraying the denitration supplement absorbent component C into a pipeline between an exhaust outlet of the SDA desulfurization tower and the bag-type dust remover through a high-pressure spray gun to serve as a supplement scheme after the SDA desulfurization and denitration, SO as to ensure that SO2And NOXThe amount of the denitration supplementary absorbent component C is 165.3-175 Kg/h. The purified flue gas is dedusted by a bag-type dust remover and then pressurized by a booster fan, the flue gas is introduced into a chimney to be discharged, and the discharged substances mainly comprise N2、CO2、H2O、O2And a small amount of CO and ash.
Example 2: the flue gas amount of the sintering flue gas is 90 ten thousand Nm3H is used as the reference value. The flue gas from the sintering machine equipment is dedusted by an electric precipitator so as to greatly reduce the amount of the flue gas, and the flue gas is subjected to air draft by a main exhaust fan and enters a flue. Simultaneously, the denitration oxidant component A is sprayed into a flue on the right side of the main exhaust fan through a high-pressure spray gun, and part of NO in the flue gas is quickly oxidized into high-valence nitrogen oxide and SO by the denitration oxidant component A2Oxidation to SO3The amount of the denitration oxidant component A consumed is 298-305 Kg/h. Then, the flue gas after oxidation treatment enters an SDA (first order SDA) desulfurization tower, meanwhile, slaked lime slurry is atomized into superfine droplets (average size is less than 50 mu m) through a rotary atomizer to spray the flue gas, and at the moment, the denitration reduction absorbent component B is also sprayed into the SDA desulfurization tower through a high-pressure spray gun; in the SDA desulfurization tower, the flue gas, the serous fluid and the denitration reduction absorbent component B are fully mixed, contacted and reacted, and the unreacted SO in the first step of the flue gas is2The acidic substances are absorbed and neutralized, and part of the high-valence nitrogen oxides are reduced into nitrogen (N)2) In the same way asThe water is evaporated, and the atomization, the absorption and the drying are rapidly finished, wherein the consumption of the denitration reduction absorbent component B is 694.6-926.2 Kg/h. And (4) discharging the dried dust-containing gas into an outlet pipeline of the SDA desulfurization tower, and outputting the generated solid by-product through an outward transportation pipeline. Spraying the denitration supplement absorbent component C into a pipeline between an exhaust outlet of the SDA desulfurization tower and the bag-type dust remover through a high-pressure spray gun to serve as a supplement scheme after the SDA desulfurization and denitration, SO as to ensure that SO2And NOXThe amount of the denitration supplementary absorbent component C is 115.8-120 Kg/h. The purified flue gas is dedusted by a bag-type dust remover and then pressurized by a booster fan, the flue gas is introduced into a chimney to be discharged, and the discharged substances mainly comprise N2、CO2、H2O、O2And a small amount of CO and ash.
Example 3: the flue gas amount of the sintering flue gas is 100 ten thousand Nm3H is used as the reference value. The flue gas from the sintering machine equipment is dedusted by an electric precipitator so as to greatly reduce the amount of the flue gas, and the flue gas is subjected to air draft by a main exhaust fan and enters a flue. Simultaneously, the denitration oxidant component A is sprayed into a flue on the right side of the main exhaust fan through a high-pressure spray gun, and part of NO in the flue gas is quickly oxidized into high-valence nitrogen oxide and SO by the denitration oxidant component A2Oxidation to SO3The amount of the denitration oxidant component A consumed is about 346.5-355 Kg/h. Then, the flue gas after oxidation treatment enters an SDA (first order SDA) desulfurization tower, meanwhile, slaked lime slurry is atomized into superfine droplets (average size is less than 50 mu m) through a rotary atomizer to spray the flue gas, and at the moment, the denitration reduction absorbent component B is also sprayed into the SDA desulfurization tower through a high-pressure spray gun; in the SDA desulfurization tower, the flue gas, the serous fluid and the denitration reduction absorbent component B are fully mixed, contacted and reacted, and the unreacted SO in the first step of the flue gas is2The acidic substances are absorbed and neutralized, and part of the high-valence nitrogen oxides are reduced into nitrogen (N)2) And simultaneously evaporating water to quickly finish atomization, absorption and drying, wherein the consumption of the denitration reduction absorbent component B is 806.5-1075.2 Kg/h. And (4) discharging the dried dust-containing gas into an outlet pipeline of the SDA desulfurization tower, and outputting the generated solid by-product through an outward transportation pipeline. Supplement absorbent group for denitrationThe part C is sprayed into a pipeline between an exhaust outlet of the SDA desulfurization tower and the bag-type dust collector through a high-pressure spray gun to be used as a supplementary scheme after the SDA desulfurization and denitrification SO as to ensure that SO2And NOXThe amount of the denitration supplementary absorbent component C is 134.4-140 Kg/h. The purified flue gas is dedusted by a bag-type dust remover and then pressurized by a booster fan, the flue gas is introduced into a chimney to be discharged, and the discharged substances mainly comprise N2、CO2、H2O、O2And a small amount of CO and ash. The desulfurization and denitrification conditions of the above examples are shown in Table 1.
TABLE 1 desulfurization and denitrification in examples 1 to 3 of the present invention
Claims (5)
1. A sintering flue gas semi-dry desulfurization and denitrification integrated device is characterized by comprising a sintering machine (1), an inlet flue gas monitoring device, an electric dust remover, a main exhaust fan, an oxidant tank (5), a rotary atomizer (6), a top tank (7), a SDA desulfurization tower (8), a reduction absorbent tank (9), a supplementary absorbent tank (10), a bag-type dust remover (11), a booster fan (12), an outlet flue gas monitoring device (13) and a chimney (14); the sintering machine (1), the inlet flue gas monitoring device, the electric dust remover, the main exhaust fan, the rotary atomizer (6), the SDA desulfurizing tower (8), the supplementary absorbent tank (10), the bag-type dust remover (11), the booster fan (12), the outlet flue gas monitoring device (13) and the chimney (14) are sequentially connected; the inlet flue gas monitoring device comprises a first inlet flue gas monitoring device (2A) and a second inlet flue gas monitoring device (2B), the electric dust remover comprises a first electric dust remover (3A) and a second electric dust remover (3B), and the main exhaust fan comprises a first main exhaust fan (4A) and a second main exhaust fan (4B); the inlet flue gas monitoring device, the electric dust remover and the main exhaust fan are respectively provided with two devices which are connected in parallel, one device is used, the first main exhaust fan (4A) and the second main exhaust fan (4B) are respectively connected with the oxidant tank (5) through two high-pressure spray guns, and the rotary atomizer (6) is connected with the upper part of the SDA desulfurization tower (8); two high-pressure spray guns are arranged in the SDA desulfurization tower (8), one is used for the next, and the two high-pressure spray guns in the SDA desulfurization tower (8) are connected with the reduction absorbent tank (9).
2. The integrated desulfurization and denitrification method of the integrated device according to claim 1, characterized by comprising the following steps:
(1) the flue gas from the sintering machine equipment is dedusted by an electric deduster to greatly reduce the amount of the flue gas, and the flue gas is subjected to air draft by a main exhaust fan and enters a flue;
(2) simultaneously, the denitration oxidant component A is sprayed into a flue on the right side of the main exhaust fan through a high-pressure spray gun, part of NO in the flue gas is quickly oxidized into high-valence nitrogen oxide by the denitration oxidant component A, and part of SO2Is also oxidized to SO3；
(3) The flue gas after oxidation treatment enters the SDA desulfurization tower (8), meanwhile, slaked lime slurry is materialized into fine fog drops through the rotary atomizer (6) to spray the flue gas, and meanwhile, a denitration reduction absorbent component B is sprayed into the SDA desulfurization tower (8) through a high-pressure spray gun; in the SDA desulfurization tower (8), the flue gas is fully mixed with the slurry and the denitration reduction absorbent component B for contact reaction, and the unreacted SO in the first step of the flue gas is completely reacted2Other acidic substances are absorbed and neutralized, part of high-valence nitrogen oxides are reduced into stable zero-valence nitrogen, and meanwhile, water is evaporated to quickly finish atomization, absorption and drying; the dried gas containing dust enters an outlet pipeline of the SDA desulfurization tower (8) to be discharged, and the generated by-product is output through an outward transportation pipeline;
(4) and spraying a denitration supplementary absorbent component C into a pipeline between an exhaust outlet of the SDA desulfurization tower (8) and the bag-type dust remover (11) through a high-pressure spray gun, dedusting the purified flue gas by the bag-type dust remover (11), pressurizing by the booster fan (12), and introducing the flue gas into the chimney (14) for discharging.
3. The integrated desulfurization and denitrification method according to claim 2, wherein the denitrification oxidant component A is an aqueous product prepared from 10-12 wt% of stable chlorine dioxide, 18-20 wt% of sodium chlorite in an alkaline system, 1-2 wt% of ferric sulfate and 1-2 wt% of sodium sulfate.
4. The integrated desulfurization and denitrification method according to claim 2, wherein the denitration reduction absorbent component B comprises 30-35 wt% of urea or paraformaldehyde, and 0.6-1.8 wt% of FeSO4·7H2O, 0.3 to 0.7 wt% of Na2S2O3Or Na2SO3And 0.01 wt% of polyvinyl alcohol 200-400.
5. The integrated desulfurization and denitrification method according to claim 2, wherein the denitrification supplement absorbent component C is an aqueous solution comprising 30-35 wt% of urea and 1-2 wt% of a ferrous complex catalyst, wherein the ferrous complex catalyst is selected from the group consisting of Fe (EDTA), Fe (NTA), dimercaptopropane sulfate, and a ferrous compound Fe (DMPS)2Any one or a mixture of two or more of them.
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