CN111054197B - Semi-dry deep desulfurization method for sulfur-containing flue gas - Google Patents
Semi-dry deep desulfurization method for sulfur-containing flue gas Download PDFInfo
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Abstract
The invention discloses a semidry deep desulfurization method for sulfur-containing flue gas, wherein a reaction tower system sequentially comprises a slurry spraying layer, a lime spraying layer and a gypsum pool from top to bottom, a desulfurized fly ash preparation system dissolves desulfurized fly ash in water to prepare desulfurized fly ash solution with the concentration of 25 percent, the desulfurized fly ash solution with the concentration of 25 percent enters a generation pool system, and most of desulfurized fly ash solution is oxidized into CaSO4The lime preparation system dissolves lime in water to prepare lime solution with the concentration of 15%, the outlet of the generation tank system is connected with the inlet of the gypsum tank, the outlet of the lime preparation system is connected with the lime spraying layer, the outlet of the gypsum tank is connected with the slurry spraying layer, and flue gas to be desulfurized is introduced into the gypsum tank of the reaction tower through the booster fan. The invention can not only completely oxidize the CaSO3 in the desulfurized fly ash by utilizing the oxidation system of the desulfurizing tower, but also can fully utilize the unreacted Ca (OH) in the desulfurization meeting2，Ca(OH)2The specific gravity of the components is about 20 percent, and the method has high utilization value.
Description
Technical Field
The invention relates to a semi-dry deep desulfurization method for sulfur-containing flue gas, in particular to a dry and semi-dry desulfurization ash oxidation process. Belongs to the technical field of chemical industry and environmental protection.
Background
The semi-dry desulfurization technology has the advantages of compact structure, small occupied area, low one-time investment, low power consumption, no waste water generation, simple and convenient maintenance and the like, and is widely applied to desulfurization engineering. The component source of the semi-dry desulfurization ash can be divided into two parts: a portion derived from fly ash, e.g. SiO2、Al2O3、FeO、Fe2O3、CaO、TiO2Etc.; the other part is derived from desulfurized and desulfurized products, CaSO3、CaSO4、Ca(OH)2、CaCO3And the like. The semidry desulfurized fly ash is mainly characterized by containing desulfurized products and a small amount of unreacted desulfurizing agent, in particularThe desulfurized fly ash contains a large amount of calcium sulfite. Therefore, the utilization mode, range and way of the desulfurized fly ash are greatly limited and restricted, and the desulfurized fly ash is difficult to be used in the traditional building material industries such as cement, concrete, brick making and the like. When CaSO is contained in the desulfurized fly ash3At higher contents, on the one hand, CaSO is formed because it is easily oxidized slowly by air4The water absorption expansion causes the drying cracking or deformation of the plate and the brick plate; CaSO on the other hand3Is extremely unstable and is easily decomposed by heat or acid to generate SO2Causing secondary pollution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a semi-dry deep desulfurization method for sulfur-containing flue gas in the prior art, solving the problem of high content of calcium sulfite in the process of resource utilization of semi-dry desulfurized ash and more effectively treating the problem of atmospheric pollution of flue gas.
The technical scheme adopted by the invention for solving the problems is as follows: a semi-dry deep desulfurization method for sulfur-containing flue gas comprises the steps of dissolving desulfurization ash in water in a desulfurization ash preparation system to prepare a desulfurization ash solution with the concentration of 25%, enabling the desulfurization ash solution with the concentration of 25% to enter a generation tank system, and adding an efficient synthetic agent into a generation tank to oxidize the desulfurization ash solution into CaSO4And keeping the solution neutral; dissolving lime in water in a lime preparation system to prepare lime solution with the concentration of 15 percent; introducing flue gas to be desulfurized into the lower part of a lime spraying layer of the reaction tower by a booster fan, pre-desulfurizing the flue gas and lime in the reaction tower, and pre-desulfurizing CaSO in the flue gas3、CaSO4In the gypsum pond of the below that the large granule was dropped by the specific gravity separator interception, flue gas and the SO2 of fractional part pass through the specific gravity separator, for the desulfurization ash solution and the lime solution that generate the pond and introduce in the gypsum pond, the layer is sprayed to the flue gas through the specific gravity separator through the thick liquid to the rethread desulfurization.
Preferably, the main components of the high-efficiency synthetic agent added into the generation pool are aqueous solution, 10% of potassium perborate, 5% of sodium hypochlorite and 2% of bromine are added, the mixture is heated in a 30-DEG water bath kettle for 30 minutes at constant temperature, the mixture is gradually added into the generation pool through a metering pump after being completely dissolved, the high-efficiency synthetic agent is neutral liquid, and Ca (OH) in the solution is not consumed2Bringing Ca (OH) in solution2With SO in flue gas2And (4) reacting.
Preferably, the desulfurized fly ash preparation system comprises a desulfurized fly ash storage bin, a first spiral weighing feeder, a desulfurized mortar liquid box stirrer and a desulfurized mortar liquid pump, wherein an inlet of the desulfurized fly ash storage bin is connected with a feeding pipe of a tank car, an outlet of the desulfurized fly ash storage bin is connected with an inlet of the first spiral weighing feeder, an inlet of the desulfurized mortar liquid box is connected with an outlet of the first spiral weighing feeder, the desulfurized mortar liquid box stirrer is installed at the top of the desulfurized mortar liquid box, an inlet of the desulfurized mortar liquid pump is connected with the desulfurized mortar liquid box, and an outlet of the desulfurized mortar liquid pump is connected with an inlet of the generating pond system.
Preferably, the lime preparation system comprises a lime storage bin, a second spiral weighing feeder, a lime slurry tank stirrer and a lime slurry pump, wherein an inlet of the lime storage bin is connected with a feeding pipe of a lime tanker, an outlet of the lime storage bin is connected with an inlet of the second spiral weighing feeder, an inlet of the lime slurry tank is connected with an outlet of the second spiral weighing feeder, a desulfurized lime slurry tank stirrer is installed at the top of the lime slurry tank, an inlet of the lime slurry pump is connected with the lime slurry tank, and an outlet of the lime slurry pump is connected with a lime spraying layer of the reaction tower system.
Preferably, the flue gas after passing through the slurry spraying layer passes through a spiral demister to remove water molecules and liquid drop impurities, the spiral demister enables the gas and the water to be gradually separated in a spiral ascending pipe, and the water content at the outlet of a chimney is kept below 3%.
Preferably, the coverage area of the spray layer in the reaction tower is 200-300%, and the retention time is 15-25 min.
Preferably, the liquid-gas ratio of the slurry spraying layer is 3-5/Nm3The liquid-gas ratio of the lime spraying layer is 4-8Nm3。
Compared with the prior art, the invention has the advantages that:
the invention uses the semidry desulfurized fly ash in the lime desulfurization system, and not only can utilize the desulfurization tower oxidation system to completely oxidize CaSO3 in the desulfurized fly ash by adding the high-efficiency synthetic agent into the generation pool for oxidizing the desulfurized fly ash,can also make full use of unreacted Ca (OH) in desulfurization meeting2，Ca(OH)2The specific gravity of the components is about 20 percent, and the method has high utilization value. Meanwhile, calcium sulfite is oxidized into calcium sulfate, so that the utilization approach of the semi-dry desulfurization ash can be greatly increased, and the utilization rate of the desulfurization ash is also improved.
Drawings
FIG. 1 is a schematic structural diagram of a system for oxidizing and deeply desulfurizing semi-dry desulfurized fly ash according to the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is described in further detail below with reference to the accompanying examples.
As shown in fig. 1, the system for oxidizing and deeply desulfurizing semi-dry desulfurized fly ash in the present embodiment includes a desulfurized fly ash preparation system, a formation pond system, a lime preparation system, a reaction tower system, and the like.
The desulfurized fly ash preparation system is used for dissolving desulfurized fly ash in water to prepare desulfurized fly ash solution with the concentration of about 25 percent. The system comprises a desulfurized fly ash storage bin 1, a first spiral weighing feeder 2, a desulfurized mortar liquid box 3, a desulfurized fly ash slurry box stirrer 4 and a desulfurized mortar liquid pump 5. The inlet of the desulfurized fly ash storage bin 1 is connected with the feeding pipe of the tank car, and the outlet of the desulfurized fly ash storage bin 1 is connected with the inlet of the first spiral weighing feeder 2. The inlet of the desulfurization mortar liquid box 3 is connected with the outlet of the first spiral weighing feeder 2, and the top of the desulfurization mortar liquid box 3 is provided with a desulfurization mortar liquid box stirrer 4. The inlet of the desulfurization mortar liquid pump 5 is connected with a desulfurization mortar liquid box 3.
The lime preparation system is characterized in that lime is dissolved in water to prepare lime solution with the concentration of about 25%. The system comprises a lime storage bin 6, a second spiral weighing feeder 7, a lime slurry tank 8, a lime slurry tank stirrer 9 and a lime slurry pump 10. The inlet of the lime storage bin 6 is connected with the feeding pipe of the lime tanker, and the outlet of the lime storage bin 6 is connected with the inlet of the second spiral weighing feeder 7. An inlet of the lime slurry tank 8 is connected with an outlet of the second spiral weighing feeder 7, and a desulfurized lime slurry tank stirrer 9 is arranged at the top of the lime slurry tank 8. The inlet of the lime slurry pump 10 is connected with the lime slurry tank 8.
The generation tank system is used for dissolving most of the desulfurized ashLiquid oxidation to CaSO4. The production pond system comprises a production pond 11, a production pond stirrer 12, an oxidation fan 13 and a gypsum slurry pump 14. The inlet of the generating tank 11 is connected with the outlet of the desulfurization mortar liquid pump 10. The inlet of the generating tank 11 is connected with the outlet of the oxidation fan 13, and the generating tank 11 is internally added with an independently developed high-efficiency synthetic agent to promote the desulfurized fly ash to quickly and effectively generate CaSO in the generating tank4。
The high-efficiency synthetic agent is neutral liquid and contains synthetic oxidant, and the proportioning concentration of the synthetic oxidant is 3%. The dosage of the catalyst per hour and the dosage of the desulfurized ash slurry are 1: 15.
The high-efficiency synthetic agent is not the traditional acidic liquid, and the acidic liquid firstly reacts with Ca (OH) in the solution under the acidic condition2Reaction, reduction of Ca (OH) in solution2Of Ca (OH) is wasted here2The subsequent deep desulfurization effect cannot be achieved. The high-efficiency synthetic agent independently developed by the company is neutral liquid and does not consume Ca (OH) in the solution2Bringing Ca (OH) in solution2With SO in flue gas2And (4) reacting.
The main components of the high-efficiency synthetic agent are aqueous solution, 10% of potassium perborate, 5% of sodium hypochlorite and 2% of bromine simple substance are added, the mixture is heated for 30 minutes in a 30-DEG water bath at constant temperature, and the mixture is gradually added into a generating tank through a metering pump after being completely dissolved.
The outlet of the generating tank 11 is connected with the inlet of a gypsum slurry pump 14, and the outlet of the gypsum slurry pump 14 is connected with the reaction tower system.
The synthesis time of the oxidation reaction of the system is 30 min.
The reaction tower system comprises a gypsum pool 15, a reaction tower oxidation fan 16, a slurry circulating pump 17, a reaction tower stirrer 18, a lime spraying layer 19, a slurry spraying layer 20, a spiral demister 21 and a specific gravity separator 22.
The flue gas to be desulfurized is introduced into the reaction tower by the booster fan 23. The pre-desulfurization is carried out with lime in the reaction tower. The two spraying layers in the reaction tower are respectively connected with the outlet of the lime slurry pump.
One spraying layer is arranged 3 meters above the flue gas inlet, and the interval between the two spraying layers is 2 m.
SO in the flue gas under the reaction of two spraying layers2Is mostly removed to generate CaSO3. After the flue gas passes through the specific gravity separator, CaSO in the flue gas3、CaSO4Large particles are intercepted and transferred into a gypsum pool below. Flue gases and small amounts of SO2The water droplets pass through the gravity separator and then through the slurry spray layer.
The height of the specific gravity separator was 1.2m, in which separator CaSO was present3、CaSO4The heavy particles have a porous barrier. Is intercepted. Residual SO2And water molecules rise spirally in the pores in the specific gravity separator.
The inlet of the slurry spraying layer is also connected with the outlet of the slurry circulating pump, and the inlet of the slurry circulating pump is connected with the outlet of the gypsum pool. Residual SO in flue gas2Unreacted Ca (OH) in the lime slurry can be neutralized by the desulfurized fly ash in the slurry spraying layer2Reaction to further reduce SO2The concentration of (c).
The flue gas enters a spiral demister to remove water molecules and liquid drop impurities. The spiral demister can gradually separate gas and moisture in the spiral ascending pipe and keep the moisture at the outlet of the chimney below 3 percent.
The outlet of the chimney reaches the ultra-low standard (35mg/min) required by the steel industry at present.
4 stirrers are arranged in the reaction tower. The outlet of the reaction tower is connected with the inlet of the discharge pump of the reaction tower, and the inlet of the reaction tower is connected with the inlet of the oxidation fan. In the gypsum pool, CaSO in the pool is generated3Used as reaction crystal seed of gypsum pool to further strengthen CaSO3Oxidized to dihydrate gypsum. The unreacted high-efficiency synthetic agent in the generation tank further leads the CaSO in the gypsum tank3Oxidized to dihydrate gypsum.
The coverage area of the spraying layer is 200-300%.
The outlet of the reactor discharge pump 24 is connected to the inlet of a gypsum cyclone 25. The outlet of the gypsum cyclone 25 is connected to the inlet of a vacuum belt conveyor 26. The outlet of the vacuum belt conveyor 26 is connected with a plaster storehouse 27, and the truck pulls away for taking out.
The retention time of the slurry in the reaction tower is 15-25 min.
The liquid-gas ratio of the slurry spraying layer is 3-5/Nm3The liquid-gas ratio of the lime spraying layer is 4-8Nm3。
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (7)
1. A semi-dry process deep desulfurization method for sulfur-containing flue gas is characterized by comprising the following steps: dissolving desulfurized ash in water in a desulfurized ash preparation system to prepare a desulfurized ash solution with the concentration of 25 percent, feeding the desulfurized ash solution with the concentration of 25 percent into a generation tank system, and adding an efficient synthetic agent into the generation tank to oxidize the desulfurized ash solution into CaSO4And keeping the solution neutral; dissolving lime in water in a lime preparation system to prepare lime solution with the concentration of 15 percent; introducing flue gas to be desulfurized into the lower part of a lime spraying layer of the reaction tower by a booster fan, pre-desulfurizing the flue gas and lime in the reaction tower, and pre-desulfurizing CaSO in the flue gas3、CaSO4Large particles are intercepted by the specific gravity separator and fall into a gypsum pool below, smoke and small part of SO2The flue gas passing through the specific gravity separator is desulfurized through a slurry spraying layer after passing through the specific gravity separator and a desulfurized ash solution and a lime solution in the gypsum tank;
the main components of the high-efficiency synthetic agent added into the generation tank are aqueous solution, 10 percent of potassium perborate, 5 percent of sodium hypochlorite and 2 percent of bromine simple substance are added, the high-efficiency synthetic agent is heated for 30 minutes at constant temperature in a water bath kettle at the temperature of 30 ℃, the high-efficiency synthetic agent is gradually added into the generation tank through a metering pump after being completely dissolved, the high-efficiency synthetic agent is neutral liquid, and Ca (OH) in the solution is not consumed2Bringing Ca (OH) in solution2With SO in flue gas2Reaction of。
2. The semi-dry process deep desulfurization method for sulfur-containing flue gas according to claim 1, characterized in that: the system for oxidizing and deeply desulfurizing semi-dry desulfurized fly ash according to claim 1, wherein: the desulfurization ash preparation system comprises a desulfurization ash storage bin, a first spiral weighing feeder, a desulfurization mortar liquid tank, a desulfurization ash slurry liquid tank stirrer and a desulfurization mortar liquid pump, wherein an inlet of the desulfurization ash storage bin is connected with a feeding pipe of a tank car, an outlet of the desulfurization ash storage bin is connected with an inlet of the first spiral weighing feeder, an inlet of the desulfurization mortar liquid tank is connected with an outlet of the first spiral weighing feeder, the desulfurization ash slurry liquid tank stirrer is installed at the top of the desulfurization mortar liquid tank, the desulfurization mortar liquid pump inlet is connected with the desulfurization mortar liquid tank, and an outlet of the desulfurization mortar liquid pump is connected with an inlet of a generation tank system.
3. The semi-dry process deep desulfurization method for sulfur-containing flue gas according to claim 1, characterized in that: the lime preparation system comprises a lime storage bin, a second spiral weighing feeder, a lime slurry tank stirrer and a lime slurry pump, wherein an inlet of the lime storage bin is connected with a feeding pipe of a lime tank truck, an outlet of the lime storage bin is connected with an inlet of the second spiral weighing feeder, an inlet of the lime slurry tank is connected with an outlet of the second spiral weighing feeder, the top of the lime slurry tank is provided with the desulfurized lime slurry tank stirrer, an inlet of the lime slurry pump is connected with the lime slurry tank, and an outlet of the lime slurry pump is connected with a lime spraying layer of the reaction tower system.
4. The semi-dry process deep desulfurization method for sulfur-containing flue gas according to claim 1, characterized in that: the generating pond system comprises a generating pond, a generating pond stirrer, an oxidation fan and a slurry pump, wherein an inlet of the generating pond is connected with an outlet of a desulfurization ash slurry pump, an inlet of the generating pond is connected with an outlet of the oxidation fan, an outlet of the generating pond is connected with an inlet of a gypsum slurry pump, and an outlet of the gypsum slurry pump is connected with a lime spraying layer of the reaction tower system.
5. The semi-dry process deep desulfurization method for sulfur-containing flue gas according to claim 1, characterized in that: the flue gas after the slurry spraying layer passes through a spiral demister to remove water molecules and liquid drop impurities, the spiral demister enables gas and water to be gradually separated in a spiral ascending pipe, and the water content at the outlet of a chimney is kept below 3%.
6. The semi-dry process deep desulfurization method for sulfur-containing flue gas according to claim 1, characterized in that: the coverage area of the spray layer in the reaction tower is 200-300%, and the retention time is 15-25 min.
7. The semi-dry process deep desulfurization method for sulfur-containing flue gas according to claim 1, characterized in that: the liquid-gas ratio of the slurry spraying layer is 3-5/Nm3The liquid-gas ratio of the lime spraying layer is 4-8Nm3。
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| CN112875740B (en) * | 2020-12-21 | 2023-04-14 | 杭州蕴泽环境科技有限公司 | System and method for preparing high-purity gypsum from semi-dry desulfurized fly ash |
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Inventor after: Zhao Haihao Inventor after: Li Juan Inventor after: Miao Shengdong Inventor after: Zhang Chengquan Inventor after: Xu Yuquan Inventor before: Zhao Haihao Inventor before: Li Juan Inventor before: Miao Shengdong Inventor before: Zhang Chengquan Inventor before: Xu Quanyu |