CN110639355A - CaCO for forced grinding3Online decomposition high-temperature flue gas desulfurization method and device - Google Patents

CaCO for forced grinding3Online decomposition high-temperature flue gas desulfurization method and device Download PDF

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Publication number
CN110639355A
CN110639355A CN201911057860.8A CN201911057860A CN110639355A CN 110639355 A CN110639355 A CN 110639355A CN 201911057860 A CN201911057860 A CN 201911057860A CN 110639355 A CN110639355 A CN 110639355A
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caco
flue gas
desulfurization
decomposition
cao
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CN110639355B (en
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张俊丰
符辉
黄妍
曹靖
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Xiangtan University
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Xiangtan University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • B01D53/508Sulfur oxides by treating the gases with solids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B02CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02CCRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C19/00Other disintegrating devices or methods
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/40Alkaline earth metal or magnesium compounds
    • B01D2251/404Alkaline earth metal or magnesium compounds of calcium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/60Inorganic bases or salts
    • B01D2251/602Oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases

Abstract

The invention discloses a CaCO for forced grinding3An on-line decomposition high-temperature flue gas desulfurization method and a device. Using CaCO3As a desulfurizer, CaCO is generated by utilizing the heat energy of high-temperature flue gas3Decomposing into CaO and reacting with SO on line2In the reaction and desulfurization process, the CaSO coated on the surface of the CaO particles is broken by adopting the rotary grinding of a grinding disc3Product shell layer for eliminating CaO and SO2Further reaction inhibition. The desulfurization reaction being carried out in an integrated reactor, comprising CaCO3Decomposing area, desulfurizing section, grate and grinding disc, where the high-temp fume without desulfurizing is fed into desulfurizing section for desulfurizing reaction, and the desulfurized high-temp fume is fed into CaCO3Continued completion of CaCO in the decomposition zone3Then the waste gas is discharged through a flue gas outlet and enters a subsequent process link. The inventionCaCO implementation with high-temperature flue gas3The online decomposition utilizes the forced grinding to realize the surface updating of CaO, so that the desulfurizer is fully utilized, the desulfurization efficiency is greatly improved, the purity of desulfurization product gypsum is ensured, the desulfurization cost is reduced, and the device has a simple structure and is convenient to implement.

Description

CaCO for forced grinding3Online decomposition high-temperature flue gas desulfurization method and device
Technical Field
The invention relates to the technical field of flue gas desulfurization, in particular to CaCO for forced grinding3An on-line decomposition high-temperature flue gas desulfurization method and a device.
Background
High-temperature flue gas such as high-temperature coal gas in coal gasification industry, high-temperature coal gas in blast furnaces and converters in metallurgical industry, high-temperature tail gas in glass industry, high-temperature waste gas of garbage incinerators and the like contains a large amount of SO2With NOXAnd the harmful components can cause the problems of acid rain, photochemical pollution and other atmospheric environment, and seriously harm the ecological environment and human health. Reduction of SO2The emission of (3) and control of atmospheric SO2Pollution and protection of the quality of the atmospheric environment are one of the important problems of environmental protection in China currently and for a long time in the future.
Flue gas desulfurization is currently controlling SO2The most efficient and widely used technique for gas discharge. The traditional desulfurization process mainly includes wet method, semi-dry method and dry method, wherein the dry method and semi-dry method generally use solid powder or particles as absorbent, including active carbon adsorption method, spray drying method and lime powder blowing method, etc., the wet method generally uses liquid as absorbent, such as ammonia method, double alkali method and limestone/lime-gypsum, etc., wherein, the most mature flue gas desulfurization technique in industry mainly includes limestone (lime) -gypsum wet method flue gas desulfurization process, which is characterized by high desulfurization efficiency (>95 percent) and high utilization rate of absorbent (>90%) can adapt to high-concentration SO2Smoke condition and low calcium-sulfur ratio (general)<1.05), desulfurized gypsum can be comprehensively utilized, and the like. The disadvantages are high capital investment cost, large water consumption, corrosive desulfurization waste water and the like. Desulfurization agent CaCO of dry desulfurization system3The slurry is changed into CaCO3The powder has high reaction speed and low treatment cost, the desulfurization product is easy to treat but has low desulfurization efficiency, and the desulfurization efficiency can be improved by spraying and humidifying, but wet ash lumps and slurry lumps are easy to form, so that the system is not smooth to operate. Patent document CN101311628 discloses a flue gas calcium spraying desulfurization process in a circulating fluidized bed boiler, which provides a desulfurization reaction of CaO powder at a temperature of less than 850 ℃ for removingSulfur method, but the price of CaO is relatively high, CaCO3Has more price competitive advantage, so CaCO is used3The replacement of CaO as a desulfurizing agent is a problem which has been recently focused, but the technology is still in the development stage and has not been widely commercially applied. In order to solve the problems of the prior art, the reaction activity of the calcium-based desulfurizer, namely CaCO, is improved3Performing on-line decomposition to make it easy to react with SO2The reaction can improve the desulfurization efficiency and the utilization rate of calcium base, and has important industrial application value. Therefore, the research and development of a new high-temperature flue gas desulfurization and purification process has important practical significance.
Disclosure of Invention
The invention aims to provide a CaCO subjected to forced grinding aiming at the defects3An on-line decomposition high-temperature flue gas desulfurization method and a device.
The technical scheme of the invention is as follows:
CaCO for forced grinding3The method for desulfurizing the fume by on-line decomposition and high-temp. adopts CaCO3As a desulfurizer, CaCO is generated by utilizing the heat energy of high-temperature flue gas3Decomposing into CaO on line and mixing with SO in flue gas2Reaction, the high-temperature flue gas which is not desulfurized enters a desulfurization section for desulfurization reaction, and the high-temperature flue gas which is desulfurized enters CaCO3Continued completion of CaCO in the decomposition zone3The decomposition is carried out, the waste gas is discharged from a flue gas outlet and enters a subsequent process link, and a grinding disc is adopted to rotate and grind in the desulfurization process to break CaSO coated on the surface of CaO particles3Product shell layer for eliminating CaO and SO2Inhibition of further reaction, promotion of CaO and SO2The reaction of (1).
Further, for decomposing CaCO on-line3The high-temperature flue gas is desulfurized high-temperature flue gas.
Further, CaCO3The ratio of the height of the decomposition zone to the height of the desulfurization zone is 1.0-1.4: 0.5 to 1.5.
Further, CaCO3CaCO in the decomposition zone3The particle size is 0.1-100 mm; and CaO in the desulfurization section is powdery, and the particle size is 0.01-10 mm.
CaCO forcibly ground by the above process3An on-line decomposition high-temperature flue gas desulfurization device comprising CaCO3Decomposition zone, desulfurization zone, grate, grinding disk, CaCO3The decomposition area is arranged at the upper part of the desulfurizing tower, the desulfurizing section is arranged at the lower part of the desulfurizing tower, and the CaCO3The decomposing area and the desulfurizing section are separated by a first furnace bridge, a second furnace bridge and a grinding disc are arranged below the desulfurizing section, the top and the bottom of the desulfurizing tower are respectively provided with a feeding section and a discharging section, CaCO3The desulfurization product is discharged from the discharge section, and the side surface of the desulfurization tower is oppositely provided with a flue gas inlet and a flue gas outlet.
Furthermore, the first grate is an arch grate, and a movable grate bar, CaCO3After decomposing into CaO on line, the CaO enters a desulfurization section through a furnace bridge.
Further, the second grate is a circular grate.
A grinding disc is arranged below the desulfurization section, and CaSO coated on the surface of CaO particles is broken through rotary grinding by adopting the grinding disc3And (4) discharging the desulfurization product through a bottom discharging section.
Further, first grate interval be 0.1 ~ 10mm, second grate interval is 0.01 ~ 1mm, and the interval of second grate is less than first grate.
The invention has the beneficial effects that:
(1) the method can remove the sulfide in the high-temperature flue gas, does not need to add an additional tail humidifying system, has simple process, low cost and convenient operation and maintenance, and the obtained desulfurization product does not slag, can be used for subsequent processes and is beneficial to realizing industrial application.
(2) Process of the invention, CaCO3The combined action of the on-line decomposition and the forced grinding of CaO obviously promotes the vulcanization reaction of CaO, thereby being beneficial to improving the desulfurization efficiency and the calcium-based utilization rate. By CaCO3The on-line decomposition of the particles obviously increases the retention time of the flue gas and strengthens the desulfurization effect; CaSO (calcium oxide) coated on the surface of CaO particles is broken through rotary grinding3Shell layer of product, SO in reactant gas2It is easier to diffuse into the interior of the particles through micropores in the surface (stratum) of the particles,thereby leading the desulfurizer to have larger contact area with the flue gas, and eliminating CaO and SO by grinding2The further reaction is hindered, the sintering of the product layer is prevented, and the further utilization of the desulfurization product is facilitated.
(3) The device adopted by the invention adopts the arched furnace bridge in the middle, so that the air inlet is more uniform than that of a combustion chamber method, and the material and space are saved. The fire bars in the arched grate can movably lean against the square frame of the grate, so that the arched grate is convenient to replace and can prevent material blockage and blanking; the spacing distance between the circular furnace bridges is smaller than that of the arched furnace bridges, so that a reaction zone is formed between the circular furnace bridges and the arched furnace bridges, and the function of moving the bed is really realized.
In summary, the invention utilizes high temperature flue gas to implement CaCO3The online decomposition utilizes the forced grinding to realize the surface updating of CaO, so that the desulfurizer is fully utilized, the desulfurization efficiency is greatly improved, the purity of desulfurization product gypsum is ensured, the desulfurization cost is reduced, and the device has a simple structure, is convenient to implement and is particularly suitable for the desulfurization treatment of high-temperature flue gas.
Drawings
FIG. 1 is a schematic view of the structure of the apparatus of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the invention is not limited thereto.
As shown in FIG. 1, the apparatus of the present invention comprises CaCO3A decomposition zone 1, a desulfurization section 2, an arch furnace bridge 3, a circular furnace bridge 4, a grinding disc 5, CaCO3The decomposition zone 1 is arranged at the upper part of the desulfurizing tower, the desulfurizing section 2 is arranged at the lower part of the desulfurizing tower, CaCO3Decomposition area 1 is separated by arch grate 3 with desulfurization section 2, and 2 below in desulfurization section are provided with circular grate 4 and abrasive disc 5, and the desulfurizing tower top and bottom set up feeding section 6 and ejection of compact section 7 respectively, and the desulfurizing tower side sets up flue gas inlet 8 and exhanst gas outlet 9 relatively. The high-temperature flue gas which is not desulfurized enters a desulfurization section 2 for desulfurization reaction, and the high-temperature flue gas which is desulfurized enters CaCO3Continued completion of CaCO in decomposition zone 13Then discharged through a flue gas outlet 9 and enters a subsequent process link. The grinding disc 5 is adopted to rotate and grind in the desulfurization processGrinding to break the CaSO coated on the surface of CaO particles3The product shell layer eliminates CaO and SO2Further reaction inhibition.
Example 1
Simulating the flue gas temperature of 700 ℃ and SO2Concentration 1000mg/Nm3Smoke amount 400Nm3H, the simulated flue gas enters the desulfurizing tower through a flue gas inlet 8, CaCO3The height of the decomposition zone 1 is 1.0m, the height of the desulfurization zone 2 is 0.5m, the particle size of the desulfurizer is 0.1mm, the flow velocity of flue gas is 3.8m/s, the flue gas after desulfurization flows out from the flue gas outlet 9, and the desulfurization efficiency is 90.1% by calculation.
Example 2
Simulating the flue gas temperature of 700 ℃ and SO2Concentration 1000mg/Nm3Smoke amount 400Nm3H, the simulated flue gas enters the desulfurizing tower through a flue gas inlet 8, CaCO3The height of the decomposition zone 1 is 1.2m, the height of the desulfurization zone 2 is 1.0m, the particle size of the desulfurizer is 0.05mm, the flow velocity of flue gas is 3.8m/s, the flue gas after desulfurization flows out from a flue gas outlet 9, and the desulfurization efficiency is calculated to be 92.3%.
Example 3
Simulating the flue gas temperature of 900 ℃ and SO2Concentration 1000mg/Nm3Smoke amount 400Nm3H, the simulated flue gas enters the desulfurizing tower through a flue gas inlet 8, CaCO3The height of the decomposition zone 1 is 1.0m, the height of the desulfurization zone 2 is 0.5m, the particle size of the desulfurizer is 0.1mm, the flow velocity of flue gas is 3.8m/s, the flue gas after desulfurization flows out from the flue gas outlet 9, and the desulfurization efficiency is calculated to be 92.7%.
Example 4
Simulating the flue gas temperature of 900 ℃ and SO2Concentration 1000mg/Nm3Smoke amount 400Nm3H, the simulated flue gas enters the desulfurizing tower through a flue gas inlet 8, CaCO3The height of the decomposition zone 1 is 1.2m, the height of the desulfurization zone 2 is 1.0m, the particle size of the desulfurizer is 0.05mm, the flow velocity of flue gas is 3.8m/s, the flue gas after desulfurization flows out from the flue gas outlet 9, and the desulfurization efficiency is 94.9% by calculation.
In the above examples, the purity of the desulfurization product gypsum was 95% or more.

Claims (8)

1. Force aGround CaCO3The on-line decomposition high-temperature flue gas desulfurization method is characterized by adopting CaCO3As a desulfurizer, CaCO is generated by utilizing the heat energy of high-temperature flue gas3Decomposing into CaO on line and mixing with SO in flue gas2Reaction, the high-temperature flue gas which is not desulfurized enters a desulfurization section for desulfurization reaction, and the high-temperature flue gas which is desulfurized enters CaCO3Continued completion of CaCO in the decomposition zone3The decomposition is carried out, the waste gas is discharged from a flue gas outlet and enters a subsequent process link, and a grinding disc is adopted to rotate and grind in the desulfurization process to break CaSO coated on the surface of CaO particles3Product shell layer for eliminating CaO and SO2Inhibition of further reaction, promotion of CaO and SO2The reaction of (1).
2. Forced ground CaCO according to claim 13The method for desulfurizing flue gas by on-line decomposition and high temperature is characterized by being used for on-line decomposition of CaCO3The high-temperature flue gas is desulfurized high-temperature flue gas.
3. Forced ground CaCO according to claim 13The method for desulfurizing the high-temperature flue gas by on-line decomposition is characterized in that CaCO3The ratio of the height of the decomposition zone to the height of the desulfurization zone is 1.0-1.4: 0.5 to 1.5.
4. Forced ground CaCO according to claim 13The method for desulfurizing the high-temperature flue gas by on-line decomposition is characterized in that CaCO3CaCO in the decomposition zone3The particle size is 0.1-100 mm; and CaO in the desulfurization section is powdery, and the particle size is 0.01-10 mm.
5. Forced grinding CaCO used in the method of any one of claims 1 to 43The on-line decomposition high-temperature flue gas desulfurization device is characterized by comprising CaCO3Decomposition zone, desulfurization zone, grate, grinding disk, CaCO3The decomposition area is arranged at the upper part of the desulfurizing tower, the desulfurizing section is arranged at the lower part of the desulfurizing tower, and the CaCO3The decomposition area is separated from the desulfurization section by a first furnace bridge, a second furnace bridge and a grinding disc are arranged below the desulfurization section, and the desulfurization section is removedThe top and the bottom of the sulfur tower are respectively provided with a feeding section and a discharging section, CaCO3The desulfurization product is discharged from the discharge section, and the side surface of the desulfurization tower is oppositely provided with a flue gas inlet and a flue gas outlet.
6. The apparatus as claimed in claim 5, wherein the first grate is an arch grate, and the movable grate, CaCO, is provided on the grate3After decomposing into CaO on line, the CaO enters a desulfurization section through a furnace bridge.
7. The apparatus of claim 5, wherein said second grate is a circular grate.
8. The apparatus as claimed in claim 5, wherein the first bridges are spaced apart by a distance of 0.1 to 10mm, the second bridges are spaced apart by a distance of 0.01 to 1mm, and the second bridges are spaced apart by a distance smaller than the first bridges.
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