CN112237816A - Rotary kiln flue gas desulfurization method and ion exchanger used for same - Google Patents
Rotary kiln flue gas desulfurization method and ion exchanger used for same Download PDFInfo
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- CN112237816A CN112237816A CN201910654405.XA CN201910654405A CN112237816A CN 112237816 A CN112237816 A CN 112237816A CN 201910654405 A CN201910654405 A CN 201910654405A CN 112237816 A CN112237816 A CN 112237816A
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- flue gas
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- regeneration
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- 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
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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
- B01D53/46—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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- 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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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
- B01D53/96—Regeneration, reactivation or recycling of reactants
Abstract
The invention discloses a rotary kiln flue gas desulfurization method and an ion exchanger used for the method, comprising the steps of enabling sulfur-containing flue gas to sequentially pass through a filtering device for absorbing large particles and an active carbon adsorption device for absorbing small particles, then enabling the sulfur-containing flue gas to enter a desulfurization tower, and enabling NaOH solution sprayed on the top of the desulfurization tower to absorb SO in the flue gas2Conversion to SO3 2‑After absorption, the water flows into a waste liquid tank from the bottom, and then flows through a regeneration tank and Ca in the regeneration tank2+Production of CaSO3Then the mixture is exposed and precipitated in a precipitation tank to be separated out, the desulfurization is completed, and clear liquid flows through Na2CO3A solution reaction tank and an ion exchanger, and calcium ions in the solution reaction tank are removed. The invention passes through the filtrationThe device and the adsorption device remove large and small particles in the flue gas, reduce the physical hard scale generated in the desulfurizing tower by using Na2CO3The solution and the ion exchanger process the regenerated NaOH solution in the regeneration tank, remove calcium ions in the regenerated NaOH solution and avoid chemical hard scale from being generated in the sulfur tower.
Description
Technical Field
The invention relates to the field of rotary kiln flue gas desulfurization, in particular to a rotary kiln flue gas desulfurization method and an ion exchanger used for the same.
Background
The dual-alkali desulfurization is to absorb SO by using alkaline clear liquid as an absorbent2And then regenerating the absorption liquid with an alkaline solution such as lime slurry. Because two different types of alkali are used in the flue gas absorption and absorption liquid treatment, the method is called a double-alkali method, the common double-alkali method is a sodium-calcium double-alkali method, theoretically, the method avoids the defect that the traditional limestone-gypsum is easy to scale, and the problems of scaling, slurry blockage and the like do not exist, however, in the actual operation, the desulfurization of a double-alkali desulfurization systemFouling of the column still frequently occurs, and some are still severe. Substances causing fouling are detected to be divided into two categories:
the first kind is physical hard scale formed by precipitate at high temperature, mainly because fine particles in flue gas are adhered to the desulfurization tower and the pipeline, and the flue gas is formed by gradual deposition after moisture is taken away by overhigh temperature;
the second type is chemical hard scale crystallized from the components in the desulfurizing tower, which mainly comprises three substances: calcium carbonate, calcium sulfite, and calcium sulfate. The main reasons are: calcium ions in the regeneration tank enter the desulfurizing tower along with the NaOH solution and enter the tail gas in the desulfurizing tower2And CO2, and then air oxidized, with crystals deposited everywhere.
The main reason is that the flue gas contains particulate matters which are not combusted sufficiently, and the regenerated NaOH solution contains a large amount of calcium ions, and the particulate matters enter the desulfurizing tower along with the solution, so that if scaling is to be prevented, the content of the particles in the flue gas entering the desulfurizing tower must be controlled, and meanwhile, the calcium ions carried in the alkali liquor flushing liquid are avoided.
Disclosure of Invention
The invention aims to provide a rotary kiln flue gas desulfurization method and an ion exchanger used for the method, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a rotary kiln flue gas desulfurization method and an ion exchanger used for the method comprise:
step 1: the sulfur-containing flue gas enters a filtering device, and a filter screen in the filtering device filters large particles contained in the sulfur-containing flue gas, which are not fully combusted, and dust:
step 2: enabling the sulfur-containing flue gas obtained in the step 1 to enter an activated carbon adsorption device, and adsorbing fine particles in the flue gas by activated carbon in the activated carbon adsorption device;
and step 3: the sulfur-containing flue gas after the step 2 enters a desulfurizing tower, NaOH solution in a NaOH liquid storage tank is sprayed from the top of the desulfurizing tower to SO in the flue gas2Absorbing to generate NaSO3And NaHSO3The treatment liquid is fed into a desulfurizing towerBottom flow enters a waste liquid pool, and desulfurized flue gas is discharged from the top of a desulfurizing tower;
and 4, step 4: introducing the treatment liquid in the waste liquid pool in the step 3 into a regeneration pool, wherein Ca (OH) in the regeneration pool2With NaSO3And NaHSO3Reacting to generate CaSO3 suspended particles and NaOH solution;
and 5: introducing the solution treated in the step 4 into a sedimentation tank for sedimentation, and separating the sediment;
step 6: extracting the supernatant in step 5 to contain Na2CO3In the reaction tank of the solution, Ca in the solution2+ and Na2CO3Reaction to form CaCO3The particles are removed by filtration after sedimentation;
and 7: and (4) introducing the solution subjected to the sedimentation treatment in the step (6) into an ion exchanger, exchanging sodium ions in sodium type cation exchange resin in the ion exchanger with the residual calcium ions in the solution, and introducing the solution treated by the ion exchanger into a NaOH liquid storage tank.
Further, the NaOH liquid storage tank in the step 3 is connected with a NaOH solution replenishing tank.
Furthermore, a limestone feeding device and a stirring device are arranged on the regeneration tank in the step 4.
Further, a PH detection device is arranged in the regeneration tank in the step 4.
Further, an aeration pipe communicated with the bottom is arranged on the sedimentation tank in the step 5.
Further, ion exchanger includes annular exchange tank, it will to vertically be provided with four in the exchange tank the even interval of exchange tank is four interval baffles, all is provided with the rack in four intervals, it places the board to be provided with the multilayer on the rack, place the board and place cation exchange resin for interior cavity and its interior, it is provided with a plurality of through-holes that pierce through from top to bottom on the board to place, all be provided with on the rack and stretch out by the top the outer bracing piece of exchange tank, the vertical axis of rotation that is provided with in center department of exchange tank, the bottom of axis of rotation is provided with drives its pivoted motor, the cover is equipped with along its gliding slider from top to bottom in the axis of rotation, the top of axis of rotation is provided with the promotion the cylinder that the slider removed, be provided with on the slider with the top fixed connection's of.
Furthermore, the four sections of the exchange tank are respectively an exchange zone, a cleaning zone, a regeneration zone and a replacement zone which are sequentially connected, circulating water is stored in the cleaning zone, sulfuric acid is stored in the regeneration zone, and NaSO is stored in the replacement zone4And (3) solution.
Compared with the prior art, the invention has the beneficial effects that: by adopting the method, the large and small particles in the flue gas are removed through the filtering device and the adsorption device, and the physical hard scale generated in the desulfurizing tower is reduced; by using Na2CO3The solution and the ion exchanger process the regenerated NaOH solution in the regeneration tank, remove calcium ions in the regenerated NaOH solution and avoid chemical hard scale from being generated in the sulfur tower.
Drawings
FIG. 1 is a schematic view of the process of the present invention,
FIG. 2 is a schematic view of the structure of an ion exchanger according to the present invention,
FIG. 3 is a schematic top view of an ion exchanger according to the present invention,
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-3, the present invention provides a technical solution: a rotary kiln flue gas desulfurization method and an ion exchanger used for the method comprise:
step 1: contain the sulphur flue gas and get into filter equipment, the filter screen among the filter equipment filters the insufficient material of large granule burning and dust that contain in the sulphur flue gas, and filter equipment is common gas filter, and large granule and partial tiny particle in the flue gas can be filtered to the filter screen in it, and partial tiny particle passes through filter equipment along with the flue gas together:
step 2: the sulfur-containing flue gas obtained in the step 1 enters an activated carbon adsorption device, activated carbon in the activated carbon adsorption device adsorbs fine particles in the flue gas, and the activated carbon adsorption device is a filter ball filled with activated carbon and adsorbs unfiltered small particulate matters in the flue gas;
and step 3: the sulfur-containing flue gas after the step 2 enters a desulfurizing tower, NaOH solution in a NaOH liquid storage tank is sprayed from the top of the desulfurizing tower to SO in the flue gas2Absorbing to generate NaSO3And NaHSO3The treating fluid flows into a waste fluid tank from the bottom of the desulfurizing tower, the desulfurized flue gas is discharged from the top of the desulfurizing tower, the NaOH solution in the NaOH solution tank is arranged at the top of the desulfurizing tower, the NaOH solution in the NaOH solution tank is pumped by a pump to enter a spray pipe to be sprayed downwards in the desulfurizing tower, the flue gas enters from the side wall of the desulfurizing tower, and SO in the downward sprayed liquid drops meets the descending sprayed liquid drops in the ascending process2The droplets are melted and the following reaction occurs;
SO2+2NaOH→Na2SO3+H2O
Na2SO3+SO2+H2O→2NaHSO3
SO2absorbed by the liquid drops, converged to the bottom of the desulfurization tower and flows into a waste liquid pool, and the arrangement of the multiple layers of spray pipes ensures that the flue gas fully contacts the liquid drops in the rising process, and the discharged flue gas meets the standard;
and 4, step 4: introducing the treatment liquid in the waste liquid pool in the step 3 into a regeneration pool, wherein Ca (OH) in the regeneration pool2With NaSO3And NaHSO3The reaction generates CaSO3 suspended particles and NaOH solution, and the regeneration of the NaOH solution is completed, and the specific reaction is as follows:
Na2SO3+Ca(OH)2+1/2H2O→NaOH+CaSO3·1/2H2O
2NaHSO3+Ca(OH)2→2NaOH+CaSO3·1/2H2O+3/2H2O；
and 5: introducing the solution treated in the step 4 into a sedimentation tank for sedimentation, separating the sediment to complete desulfurization, and recycling the desulfurization product;
step 6: extracting the supernatant in step 5 to contain Na2CO3In the reaction tank of the solution, Ca in the solution2+With Na2CO3Reaction to form CaCO3The particles are removed by filtration after sedimentation, and the specific reaction is as follows:
Ca2++CO3 2-→CaCO3
formation of most of the calcium ions as CaCO3Precipitating, wherein the rest part cannot be removed and continuously flows along with the solution;
and 7: and (3) introducing the solution subjected to the sedimentation treatment in the step (6) into an ion exchanger, exchanging sodium ions in cation exchange resin in the ion exchanger with calcium ions remained in the solution, introducing the solution subjected to the treatment by the ion exchanger into a NaOH liquid storage tank, adsorbing the calcium ions in the solution by the cation exchange resin in the ion exchanger and releasing the sodium ions, further removing the calcium ions in the regenerated liquid passing through the ion exchanger, and avoiding backflow into the desulfurizing tower.
And (3) connecting the NaOH liquid storage tank in the step (3) with a NaOH solution supplementing tank, and supplementing in time when the amount of NaOH in the liquid storage tank is insufficient.
The regeneration tank in the step 4 is provided with a limestone feeding device, the regeneration tank is internally provided with a solution stirring device and a PH detection device, the PH detection device monitors the PH value in the regeneration tank, when the PH value is not enough, limestone is added in time, and Ca (OH) in the regeneration tank is ensured2The stirring device ensures that the limestone is uniformly dispersed in the adding process, and Ca (OH) at each position in the regeneration tank2The content of the sulfur is consistent, and incomplete desulfurization is avoided.
The sedimentation tank in the step 5 is provided with an aeration pipe which is introduced into the bottom, and the aeration pipe is introduced with air, so that the product in the sedimentation tank is gypsum, and the concrete reaction is as follows:
2CaSO3·1/2H2O+O2+3H2O→2(CaSO4·2H2O)
then the gypsum is recycled.
The ion exchanger comprises an annular exchange tank 1, four partition plates 2 which divide the exchange tank into four sections evenly are vertically arranged in the exchange tank 1, a placing frame 3 is arranged in each of the four sections, the placing racks 3 are all provided with a plurality of layers of placing plates 4, the placing plates 4 are hollow and are internally provided with cation exchange resin 5, a plurality of through holes which penetrate up and down are arranged on the placing plate, supporting rods 6 which extend out of the exchange tank 1 from the top are arranged on the placing frames 3, a rotating shaft 7 is vertically arranged at the center of the exchange tank 1, a motor for driving the rotating shaft to rotate is arranged at the bottom of the rotating shaft, a sliding block 8 sliding up and down along the rotating shaft 7 is sleeved on the rotating shaft 7, an air cylinder 9 pushing the sliding block 8 to move is arranged at the top end of the rotating shaft 7, and the sliding block 8 is provided with a connecting rod 10 fixedly connected with the top end of the supporting rod 6.
The four sections of the exchange tank 1 are respectively an exchange zone 11, a cleaning zone 12, a regeneration zone 13 and a replacement zone 14 which are sequentially connected, circulating water is stored in the cleaning zone 12, the circulating water circularly flows in a reservoir and the cleaning zone through a circulating water pump, sulfuric acid is stored in the regeneration zone 13, and NaSO is stored in the replacement zone 144Solution, sulfuric acid and NaSO4The solution is added at regular time to ensure the concentration of the solution and the solution.
The regenerated liquid entering the ion exchanger enters an exchange area, the regenerated liquid passes through a placing plate in the exchange area along with the flowing of the regenerated liquid, cation exchange resin in the placing plate releases sodium ions and adsorbs calcium ions in the solution, a plurality of layers of placing plates ensure that the calcium ions in the solution are adsorbed to the maximum extent, the calcium ions are prevented from flowing back to a NaOH liquid storage tank, the placing plate in a cleaning area is washed by circularly flowing clear water, alkali liquor attached to the placing plate is washed away, the cation exchange resin in the placing plate in the regeneration area is replaced by hydrogen ions under the replacement of sulfuric acid solution, the activity of the cation exchange resin in the replacement area is recovered again, and the cation exchange resin in the replacement area is subjected to NaSO4Under the action of the solution, hydrogen ions are replaced by sodium ions; along with the continuous calcium ion absorption of cation exchange resin in the exchange area, the absorption effect is worse and worse, and the cylinder pulls the sliding block after a period of timeRise and drive the rack and rise the top to the exchange tank, then control motor drives axis of rotation and the rotatory 90 degrees of rack, and the rack in the exchange area rotates the top of wasing the district originally, promotes through the cylinder and descends, and in the rack descends and gets into the exchange tank, so circulation for calcium ion in the exchange area is continuously adsorbed, and cation exchange resin can not lose the activity, and the reaction that each district takes place is as follows:
an exchange area: 2R-SO3Na+Ca2+→(R-SO3)2Ca+2Na+
A regeneration zone: (R-SO3)2Ca+2H+→2R-SO3H+Ca2+
Replacement region R-SO3H + Na+→R-SO3Na+H+
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The rotary kiln flue gas desulfurization method is characterized by comprising the following steps of:
step 1: the sulfur-containing flue gas enters a filtering device, and a filter screen in the filtering device filters large particles contained in the sulfur-containing flue gas, which are not fully combusted, and dust:
step 2: enabling the sulfur-containing flue gas obtained in the step 1 to enter an activated carbon adsorption device, and adsorbing fine particles in the flue gas by activated carbon in the activated carbon adsorption device;
and step 3: the sulfur-containing flue gas after the step 2 enters a desulfurizing tower, NaOH solution in a NaOH liquid storage tank is sprayed from the top of the desulfurizing tower to SO in the flue gas2Absorbing to generate NaSO3And NaHSO3The treatment liquid flows into a waste liquid pool from the bottom of the desulfurizing tower, and the desulfurized flue gas is discharged from the top of the desulfurizing tower;
and 4, step 4: introducing the treatment liquid in the waste liquid pool in the step 3 into a regeneration pool, wherein Ca (OH) in the regeneration pool2With NaSO3And NaHSO3Reaction to produce CaSO3Suspended particles and NaOH solution;
and 5: introducing the solution treated in the step 4 into a sedimentation tank for sedimentation, and separating the sediment;
step 6: extracting the supernatant in step 5 to contain Na2CO3In the reaction tank of the solution, Ca in the solution2+With Na2CO3Reaction to form CaCO3The particles are removed by filtration after sedimentation;
and 7: and (4) introducing the solution subjected to the sedimentation treatment in the step (6) into an ion exchanger, exchanging sodium ions in cation exchange resin in the ion exchanger with the residual calcium ions in the solution, and introducing the solution treated by the ion exchanger into a NaOH liquid storage tank.
2. The rotary kiln double alkali flue gas desulfurization method as claimed in claim 1, wherein the NaOH solution storage tank in step 3 is connected to a NaOH solution replenishing tank.
3. The rotary kiln flue gas desulfurization method as claimed in claim 1, wherein the regeneration tank in step 4 is provided with a limestone feeding device and a stirring device.
4. The rotary kiln flue gas desulfurization method as claimed in claim 1, wherein a PH detection device is disposed in the regeneration tank in step 4.
5. The rotary kiln flue gas desulfurization method as claimed in claim 1, wherein the settling tank in the step 5 is provided with an aeration pipe which is introduced into the bottom.
6. An ion exchanger used in the above step 7, characterized in that the ion exchanger comprises an annular exchange tank, four partition plates are vertically arranged in the exchange tank and divide the exchange tank into four sections, the four sections are all provided with placing racks, the placing rack is provided with a plurality of layers of placing plates which are hollow and are internally provided with cation exchange resin, a plurality of through holes which penetrate up and down are arranged on the placing plate, supporting rods which extend out of the exchange tank from the top are arranged on the placing rack, a rotating shaft is vertically arranged at the center of the exchange tank, a motor for driving the rotating shaft to rotate is arranged at the bottom of the rotating shaft, the rotating shaft is sleeved with a sliding block which slides up and down along the rotating shaft, the top end of the rotating shaft is provided with an air cylinder which pushes the sliding block to move, and the sliding block is provided with a connecting rod which is fixedly connected with the top end of the supporting rod.
7. The ion exchanger as claimed in claim 6, wherein the four sections of the exchange tank are an exchange zone, a cleaning zone, a regeneration zone and a replacement zone which are connected in sequence, the cleaning zone is stored with circulating water, the regeneration zone is stored with sulfuric acid, and the replacement zone is stored with NaSO4And (3) solution.
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| US3944649A (en) * | 1973-12-13 | 1976-03-16 | Combustion Equipment Associates, Inc. | Multistage process for removing sulfur dioxide from stack gases |
| JPH0699026A (en) * | 1991-02-12 | 1994-04-12 | Mitsubishi Heavy Ind Ltd | Treatment of waste gas |
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