CN110963507A - Ammonia water ammonia production system and process for coke oven flue gas denitration - Google Patents
Ammonia water ammonia production system and process for coke oven flue gas denitration Download PDFInfo
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- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/10—Separation of ammonia from ammonia liquors, e.g. gas liquors
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- 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
- B01D53/86—Catalytic processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides an ammonia water ammonia preparation system for denitration of coke oven flue gas, which comprises the following steps: the ammonia stripping tower comprises a tower body, and a demister, a nozzle, a packing layer, a tower kettle and an air inlet which are sequentially arranged in the tower body from top to bottom; the ammonia water conveying system comprises a concentrated ammonia water storage tank, a concentrated ammonia water conveying pump and a concentrated ammonia water preheating device; the air conveying system comprises a dilution fan and an air preheater; the ammonia gas discharge system is communicated with the ammonia gas stripping tower; the ammonia water circulating pump is communicated with the tower kettle and the nozzle; the ammonia water discharge system comprises a dilute ammonia water return pump, a filter, a reverse osmosis system and a concentrated solution discharge pump. The method for preparing ammonia gas by blowing off ammonia water for the first time provides a reducing agent for the SCR denitration system, the preparation and dilution processes of ammonia gas are completed in the same equipment, the ammonia gas with the volume fraction of less than 5% is prepared, the process flow is simplified, the investment cost is reduced, the system stability and adaptability are high, the automation degree is high, the energy is saved, the environment is protected, and the method is economical and practical.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to an ammonia water-ammonia making system and process for denitration of coke oven flue gas.
Background
In recent years, environmental problems such as acid rain, dust haze, photochemical smog and the like caused by pollutants such as nitrogen oxides and the like are increasingly prominent, and environmental protection requirements are gradually increased. Boilers and other equipment in various industries such as electric power, chemical industry, steel, cement, waste incineration and the like, such as cement kilns, sintering machines and the like are provided with flue gas denitration devices. The SCR flue gas denitration method, i.e., the selective catalytic reduction flue gas denitration method, is gradually becoming the mainstream technology for nitrogen oxide treatment. At present, urea or liquid ammonia is commonly used as a reducing agent in an SCR flue gas denitration method. The urea is convenient to transport and store, but the energy consumption for ammonia production is high; the liquid ammonia has high reaction efficiency and low ammonia consumption, but has flammable, toxic and dangerous properties, strict requirements on transportation and storage and inconvenient use. The ammonia water has low price and safe use, is one of the products produced by the coke-oven plant, and is an important raw material for the coking, cold drum, desulfurization and other working sections of the coke-oven plant. The inside of the coking plant is provided with a circulating ammonia water using unit and a residual ammonia water treating unit, so that the comprehensive utilization of ammonia water and the standard-reaching discharge of ammonia-containing wastewater can be ensured. Therefore, the ammonia water is used as the reducing agent for the denitration of the coke oven flue gas, the raw materials can be used locally, the existing conditions can be fully combined, and the investment and the operation cost are reduced. However, any reducing agent requires a method of converting ammonia, which is present in a liquid or other form, into ammonia gas. The existing technology for preparing ammonia gas from ammonia water is to heat and evaporate the ammonia water, dilute the evaporated ammonia gas with air, and then enter an SCR denitration system; or the ammonia water is atomized and then directly sprayed into the high-temperature flue gas, and the ammonia water and the water are evaporated together.
Chinese patent CN204261549U relates to a low-temperature coke oven flue waste gas purification device, and the device adopts ammonia gas generated by evaporating ammonia water as a denitration reducing agent, but a large amount of water and ammonia gas are evaporated together in the evaporation process, the latent heat of vaporization of the water is up to 2500kJ/kg, the system energy consumption is very high, and the economical efficiency is poor.
Chinese patent CN106145159A relates to a system and a method for preparing ammonia gas from ammonia water for SCR denitration in a cement plant, wherein atomized ammonia water is evaporated by latent heat of saturated steam of not less than 150 ℃, the consumption of the saturated steam is low, and the cost is reduced to a certain extent, but the system is only suitable for ammonia water with the concentration of 15-30%, because the latent heat of evaporation of ammonia water with lower concentration is closer to water, the required steam amount is obviously increased.
Chinese patent CN103803583A relates to a system for producing ammonia gas by evaporating ammonia water and a control method thereof, the main equipment is a row of tubular heat exchangers, the ammonia water is heated to 60-90 ℃ by steam to evaporate the ammonia gas, at the moment, the water component in the ammonia water does not reach the boiling point, the evaporation amount is little, the entrainment of water cannot be avoided in the process of ammonia production, demisting measures are not provided inside and outside the equipment, and the ammonia gas is easy to dewfall at the temperature to corrode the pipeline and the equipment; more seriously, the system discharges a large amount of 0.1-5% diluted ammonia water, belongs to ammonia nitrogen wastewater, and can discharge the ammonia water only after strict treatment. As the explosion limit of the ammonia gas is 15-28%, in order to ensure safety and uniform distribution, the ammonia gas must be diluted to a volume fraction lower than 5% before being injected into the flue, so that the ammonia gas preparation equipment and the ammonia gas preparation equipment in the patent also need an additional dilution unit, which increases the system investment and energy consumption to a certain extent and increases the operation complexity.
Chinese patent CN104548933A relates to a supply device and method for reducing agent for ammonia production from ammonia water for SCR denitration, which uses the flue gas heat at the inlet of the SCR denitration device as the heat source for heating air, and chinese patent CN10705119A relates to an ammonia production system from ammonia water for high efficiency SCR denitration system, which uses the flue gas heat inside the SCR denitration device as the heat source for heating air. In both methods, the air is heated to more than 250 ℃ by using the waste heat of the flue gas, so that the ammonia water is completely evaporated by the high-temperature air, and the effect of diluting the ammonia gas is achieved. Because an external heat source is not adopted, the energy consumption cost for ammonia production can be reduced to a certain extent. However, because ammonia and water in the ammonia water are all evaporated, the energy consumption of latent heat of vaporization is large, and the energy consumption is large for denitration of large-capacity flue gas. In addition, for a coke-oven plant, the temperature of the coke-oven flue gas is generally 140-280 ℃, the air is difficult to be heated to more than 250 ℃ by utilizing the heat of the coke-oven flue gas, and an external heat source needs to be introduced, so that the complexity and the energy consumption of the system are increased.
Chinese patent CN105413459A relates to a sintering machine flue gas ammonia water denitrator and a denitration method, and the sintering machine denitration also belongs to low-temperature denitration; meanwhile, chinese patent CN106422772A relates to an ammonia water gasification system for SCR flue gas denitration. In both methods, ammonia water is atomized in a certain mode and then directly sprayed into a flue, and ammonia water is evaporated by using flue gas with the temperature of above 120 ℃, but a large amount of water is brought into a denitration system, and the flue gas temperature is reduced by using the waste heat of the flue gas as a heat source for evaporating the ammonia water no matter the ammonia water is evaporated outside or inside the flue. Under the condition that the ammonia consumption of the denitration system is certain, the lower the concentration of the used ammonia water is, the larger the flow of the needed ammonia water is, and meanwhile, the larger the evaporated water amount is, the more obvious the reduction of the flue gas temperature is.
At present, a catalyst used for low-temperature denitration is generally sensitive to temperature change and poor in water resistance, and the activity of the catalyst is reduced due to reduction of flue gas temperature and increase of water content, so that serious problems such as excessive emission concentration of nitrogen oxides are caused, and the application of a method for preparing ammonia gas by evaporating ammonia water in the field of low-temperature denitration is limited.
Disclosure of Invention
The invention provides an ammonia water-ammonia making system and process for coke oven flue gas denitration, which solve the problems of high operation energy consumption, high water content in ammonia gas, inapplicability to low-concentration ammonia water and low-temperature denitration and the like in the prior art.
The technical scheme of the invention is realized as follows:
an ammonia water system ammonia system for denitration of coke oven flue gas, comprising:
the ammonia stripping tower comprises a tower body, a demister, a nozzle, a filler layer, a tower kettle and an air inlet, wherein the demister, the nozzle, the filler layer and the tower kettle are sequentially arranged in the tower body from top to bottom, and the air inlet is arranged between the tower kettle and the filler layer;
the ammonia water conveying system comprises a concentrated ammonia water storage tank, a concentrated ammonia water conveying pump and a concentrated ammonia water preheating device, wherein the concentrated ammonia water preheating device is communicated with the nozzle and the concentrated ammonia water conveying pump, and the concentrated ammonia water conveying pump is communicated with the concentrated ammonia water storage tank;
an air delivery system including a dilution fan and an air preheater, the air preheater in communication with the dilution fan and the air inlet;
the ammonia gas discharge system is communicated with the ammonia gas stripping tower;
the ammonia water circulating pump is communicated with the tower kettle and the nozzle;
the ammonia water discharge system comprises a dilute ammonia water return pump, a filter, a reverse osmosis system and a concentrated solution discharge pump, wherein the concentrated solution discharge pump is communicated with the reverse osmosis system, the reverse osmosis system is communicated with the economizer and the filter, the filter is communicated with the dilute ammonia water return pump, and the dilute ammonia water return pump is communicated with the tower kettle.
Further, the demister comprises a wire mesh demister and a baffle plate demister, and the wire mesh demister and the baffle plate demister are sequentially arranged in the tower body from top to bottom.
Further, the strong ammonia water preheating device comprises an energy saver and a strong ammonia water preheater, the strong ammonia water preheater is communicated with the nozzle and the energy saver, and the energy saver is communicated with the strong ammonia water delivery pump.
Further, the ammonia gas discharge system includes ammonia buffer tank and ammonia draught fan, the ammonia draught fan with ammonia buffer tank intercommunication, the ammonia buffer tank with the ammonia blows off the tower intercommunication.
Further, the reverse osmosis system comprises a reverse osmosis booster pump and a reverse osmosis device, the reverse osmosis device is communicated with the energy saver and the reverse osmosis booster pump, and the reverse osmosis booster pump is communicated with the filter.
Further, the filter comprises a multi-media filter and a cartridge filter, the cartridge filter is communicated with the reverse osmosis system and the multi-media filter, and the multi-media filter is communicated with the dilute ammonia water return pump.
The method for preparing ammonia from ammonia water for denitration of coke oven flue gas based on the ammonia preparation system comprises the following steps:
preheating concentrated ammonia water to a preset temperature, atomizing the preheated concentrated ammonia water, and spraying the atomized concentrated ammonia water into the ammonia stripping tower;
preheating air to a preset temperature, and feeding the preheated air into the ammonia stripping tower;
the atomized ammonia water and air are in countercurrent contact in the ammonia gas stripping tower for stripping, so that ammonia in the ammonia water is continuously transferred to a gas phase to become ammonia gas, and the volume fraction of the ammonia gas is diluted to be less than or equal to 5% by the air;
the ammonia diluted by air is discharged from the top of the ammonia stripping tower after entrained liquid drops are removed, and the discharged ammonia is conveyed to an SCR denitration system after the pressure is stabilized through buffering;
the dilute ammonia water generated in the stripping process is re-atomized and then enters the ammonia stripping tower again to fully release the ammonia in the ammonia water;
the dilute ammonia water reaching the discharge concentration is discharged.
Further, when the concentration of the strong ammonia water is 5-8% or the concentration of the weak ammonia water after stripping is 0.1-1%, the stripping is a vacuum air stripping process, the temperature of the strong ammonia water in the vacuum air stripping process is 40-50 ℃, the temperature of the air is 60-80 ℃, the vacuum degree is 0.01-0.05 Mpa, the circulation rate is 5-20 times, and the operation air speed for removing entrained liquid drops is 6-9 m/s.
Further, when the concentration of the strong ammonia water is 8-30% or the concentration of the weak ammonia water after stripping is 1-3%, the stripping is a normal-pressure air stripping process, the temperature of the strong ammonia water in the normal-pressure air stripping process is 20 ℃, the temperature of the air is 50-60 ℃, the circulation rate is 1-5 times, and the operation air speed for removing entrained liquid drops is 3-5 m/s.
Further, dilute ammonia water reaching the discharge concentration is output to a coking plant for recycling, impurities are filtered out in the other path, acid is added to adjust the pH value to be 5-7, reverse osmosis is carried out through a brackish water reverse osmosis membrane, the reverse osmosis recovery rate is 60-90%, the reverse osmosis water production temperature is 50-60 ℃, reverse osmosis water production exchanges heat with concentrated ammonia water preheated to the preset temperature, sensible heat of the reverse osmosis water production is recovered and then is reduced to 30 ℃, meanwhile, the reverse osmosis water production utilizes the sensible heat to heat the concentrated ammonia water to 40-50 ℃, and the reverse osmosis water production and the concentrated ammonia water exchange heat and then are recycled as reclaimed water; and (4) outputting the reverse osmosis concentrated water to a residual ammonia water treatment unit in a coking plant, and recovering ammonia in the residual ammonia water for post-treatment until the ammonia reaches the standard and is discharged.
The invention has the beneficial effects that:
1. the method for preparing ammonia gas by blowing off ammonia water for the first time provides a reducing agent for the SCR denitration system, the preparation and dilution processes of ammonia gas are completed in the same equipment, the ammonia in the ammonia water is transferred to a gas phase by using an air blowing off method, the dilution is completed immediately, the volume fraction of the prepared ammonia gas is lower than 5%, the process flow is simplified, and the investment cost is reduced.
2. The invention sets a reasonable control mode, sets process operation parameters such as temperature, vacuum degree and circulation rate of the system, ensures the full release of ammonia gas, and ensures that the system can use ammonia water with the concentration of 5-30% as raw materials.
3. The ammonia gas is prepared below the boiling point temperature of water, so that a large amount of evaporation of water is avoided, the energy consumption cost for ammonia preparation is reduced, the system is provided with the two-stage demister, the operating speed of the demister is set, good demisting and dewatering effects are guaranteed to be kept under normal pressure and vacuum conditions, the adverse effects of water on low-temperature catalysts and the temperature of flue gas are reduced to the maximum degree, and compared with a method for preparing ammonia gas by evaporating ammonia water, the system has good applicability to low-temperature denitration.
4. The method fully combines the existing process of the coking plant, realizes the effective utilization of resources, reduces the emission of pollutants to the maximum extent, and enters a circulating ammonia water using unit in the coking plant for recycling when the concentration of the emitted ammonia water is 1-3%; when the discharge concentration is 0.1-1%, most of water is recycled through the reverse osmosis system, most of heat is recycled through the energy saver, and only a small amount of concentrated solution is conveyed to the residual ammonia water treatment unit in the coking plant, so that the energy-saving and environment-friendly effects are achieved, and the energy-saving and environment-friendly effects are achieved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an ammonia water-to-ammonia system for denitration of coke oven flue gas.
In the figure:
1. an ammonia stripping tower; 101. a wire mesh demister; 102. a baffle demister; 103. a nozzle; 104. a filler layer; 105. a tower kettle; 2. a concentrated ammonia storage tank; 3. a concentrated ammonia water delivery pump; 4. an energy saver; 5. a concentrated ammonia water preheater; 6. a dilution fan; 7. an air preheater; 8. an ammonia water circulating pump; 9. an ammonia buffer tank; 10. an ammonia draught fan; 11. returning the dilute ammonia water to the pump; 12. a multi-media filter; 13. a cartridge filter; 14. a reverse osmosis booster pump; 15. a reverse osmosis unit; 16. a concentrate discharge pump; 17. the ammonia water system control module; 1701. a dense ammonia water densimeter; 1702. a concentrated ammonia water regulating valve; 1703. a concentrated ammonia water flow meter; 1704. a concentrated ammonia water thermometer; 1705. a dilute ammonia water densimeter; 1706. an air regulating valve; 1707. an air flow meter; 1708. an air thermometer; 1709. an ammonia gas pressure sensor; 18. SCR deNOx systems control module.
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.
As shown in FIG. 1, the ammonia water-ammonia making system for denitration of coke oven flue gas, provided by the invention, comprises:
the ammonia stripping tower 1 comprises a tower body, a demister, a nozzle 103, a filler layer 104, a tower kettle 105 and an air inlet arranged between the tower kettle 105 and the filler layer 104, wherein the demister, the nozzle and the filler layer 104 are sequentially arranged in the tower body from top to bottom;
the ammonia water conveying system comprises a concentrated ammonia water storage tank 2, a concentrated ammonia water conveying pump 3 and a concentrated ammonia water preheating device, wherein the concentrated ammonia water preheating device is communicated with a nozzle 103 and the concentrated ammonia water conveying pump 3, and the concentrated ammonia water conveying pump 3 is communicated with the concentrated ammonia water storage tank 2;
the air conveying system comprises a dilution fan 6 and an air preheater 7, and the air preheater 7 is communicated with the dilution fan 6 and an air inlet;
the ammonia gas discharge system is communicated with the ammonia gas stripping tower 1;
an ammonia water circulating pump 8 communicated with the tower kettle 105 and the nozzle 103;
the ammonia water discharge system comprises a dilute ammonia water return pump 11, a filter, a reverse osmosis system and a concentrated solution discharge pump 16, wherein the concentrated solution discharge pump 16 is communicated with the reverse osmosis system, the reverse osmosis system is communicated with the economizer 4 and the filter, the filter is communicated with the dilute ammonia water return pump 11, and the dilute ammonia water return pump 11 is communicated with the tower kettle 105.
The ammonia water system for denitration of coke oven flue gas, provided by the invention, can further comprise an ammonia water system control module 17, and a concentrated ammonia water densimeter 1701, a concentrated ammonia water regulating valve 1702, a concentrated ammonia water flowmeter 1703, a concentrated ammonia water thermometer 1704, a dilute ammonia water densimeter 1705, an air regulating valve 1706, an air flowmeter 1707, an air thermometer 1708, an ammonia pressure sensor 1709 and an SCR denitration system control module 18 which are in communication connection with the ammonia water system control module 17, wherein the functions and corresponding control methods are as follows:
1. before the system is started, the concentration of the strong ammonia water in the strong ammonia water storage tank 2 is monitored by a strong ammonia water densimeter 1701 and fed back to the ammonia water-to-ammonia system control module 17; the emission concentration of the dilute ammonia water is manually input to the ammonia water ammonia production system control module 17 as a design value.
2. According to the ammonia consumption obtained from the SCR denitration system control module 18 and the concentrations of the strong ammonia water and the weak ammonia water, the ammonia water system control module 17 calculates the strong ammonia water flow, and the strong ammonia water flow is adjusted by controlling the opening of the strong ammonia water adjusting valve 1702.
3. According to the concentration of the strong and weak ammonia water, the ammonia water system control module 17 selects the system operation temperature and the vacuum degree, and heats the strong ammonia water and the air to the required temperature by controlling the strong ammonia water preheating device, specifically the strong ammonia water preheater 5 and the air preheater 7; the ammonia draught fan 10 is adjusted through frequency conversion, and the vacuum degree of the system is adjusted.
4. According to the emission concentration of the dilute ammonia water, the circulation multiplying power is selected by the ammonia water ammonia preparation system control module 17, and the circulation multiplying power is adjusted by adjusting the ammonia water circulating pump 8 through frequency conversion.
5. According to the ammonia consumption and the concentration of the diluted ammonia gas obtained from the SCR denitration system control module 18, specifically, the volume fraction of the concentration of the diluted ammonia gas is not higher than 5%, the air flow is calculated by the ammonia water ammonia production system control module 17, and the air flow is adjusted by controlling the opening of the air adjusting valve 1706.
6. The concentration of the dilute ammonia water at the bottom of the tower kettle 105 is monitored by a dilute ammonia water densimeter 1705, after the designed discharge concentration is reached, a dilute ammonia water return pump 11 is started, and the dilute ammonia water is conveyed to a circulating ammonia water using unit or a reverse osmosis system, specifically a reverse osmosis device 15 of the reverse osmosis system.
7. After the dilute ammonia water begins to be discharged, the concentrations of the concentrated ammonia water and the dilute ammonia water are respectively monitored by a concentrated ammonia water densimeter 1701 and a dilute ammonia water densimeter 1705, and the concentrations are fed back to an ammonia water-to-ammonia system control module 17; the control module 17 of the ammonia water system monitors, records and adjusts various operation parameters.
The demister comprises a wire mesh demister 101 and a baffle demister 102, and the wire mesh demister 101 and the baffle demister 102 are sequentially arranged in the tower body from top to bottom.
Wherein, concentrated ammonia water preheating device includes economizer 4 and concentrated ammonia water preheater 5, and concentrated ammonia water preheater 5 communicates with nozzle 103 and economizer 4, and economizer 4 communicates with concentrated ammonia water delivery pump 3.
Wherein, ammonia discharge system includes ammonia buffer tank 9 and ammonia draught fan 10, and ammonia draught fan 10 and ammonia buffer tank 9 intercommunication, ammonia buffer tank 9 and ammonia stripping tower 1 intercommunication.
The reverse osmosis system comprises a reverse osmosis booster pump 14 and a reverse osmosis device 15, the reverse osmosis device 15 is communicated with the economizer 4 and the reverse osmosis booster pump 14, and the reverse osmosis booster pump 14 is communicated with the filter.
Wherein, the filter includes a multi-media filter 12 and a cartridge filter 13, the cartridge filter 13 is communicated with the reverse osmosis system and the multi-media filter 12, and the multi-media filter 12 is communicated with the diluted ammonia water return pump 11.
The ammonia water ammonia preparation system for the denitration of the coke oven flue gas disclosed by the invention has the following working process:
1. conveying the strong ammonia water in the strong ammonia water storage tank 2 by a strong ammonia water conveying pump 3, and preheating to a required temperature after sequentially passing through an energy saver 4 and a strong ammonia water preheater 5; the preheated strong ammonia water is conveyed to a nozzle 103, atomized and sprayed into an ammonia stripping tower 1; air is conveyed into an air preheater 7 by a dilution fan 6, and the preheated air enters an ammonia stripping tower 1 through an air inlet between a filler layer 104 and a tower kettle 105; the ammonia water and the air are in countercurrent contact in the packing layer, so that the ammonia gas in the ammonia water is continuously transferred to a gas phase and is diluted by the air until the volume fraction is lower than 5%;
2. the diluted ammonia gas passes through a baffle plate demister 102 and a wire mesh demister 101 in sequence, entrained liquid drops are removed, the ammonia gas is discharged from the top of an ammonia gas stripping tower 1, then the ammonia gas enters an ammonia gas buffer tank 9, and the ammonia gas is conveyed to an SCR denitration system by an ammonia gas induced draft fan 10 after the pressure is stabilized;
3. dilute ammonia water generated in the stripping process is stored in a tower kettle 105, continuously circulates to a nozzle 103 under the action of an ammonia water circulating pump 8, re-atomizes and then enters an ammonia gas stripping tower 1 again to ensure that ammonia in the ammonia water is fully released;
4. the dilute ammonia water reaching the discharge concentration is discharged from the bottom of the ammonia stripping tower 1, and two paths of water can be selected: one path is output to a circulating ammonia water using unit in a coking plant through a dilute ammonia water return pump 11, the other path is output to a multi-media filter 12 and a security filter 13 through the dilute ammonia water return pump 11, impurities in the water are filtered out and then are conveyed to a reverse osmosis device 15 through a reverse osmosis booster pump 14, reverse osmosis produced water enters an energy saver 4 to exchange heat with concentrated ammonia water and then is recycled as reclaimed water, the reverse osmosis concentrated water is output to a residual ammonia water processing unit in the coking plant through a concentrated water discharge pump 16, and after ammonia in the water is recovered, the water is processed until the water reaches the standard and is discharged.
The invention also provides a method for preparing ammonia from ammonia water for denitration of coke oven flue gas based on the ammonia water preparation system, which comprises the following steps:
preheating concentrated ammonia water to a preset temperature, atomizing the preheated concentrated ammonia water, and spraying the atomized concentrated ammonia water into an ammonia stripping tower 1;
preheating air to a preset temperature, and feeding the preheated air into an ammonia stripping tower 1;
the atomized ammonia water and air are in countercurrent contact in an ammonia gas stripping tower 1 for stripping, so that ammonia in the ammonia water is continuously transferred to a gas phase to become ammonia gas, and meanwhile, the volume fraction of the ammonia gas is diluted to be less than or equal to 5% by the air;
the ammonia diluted by air is discharged from the top of the ammonia stripping tower 1 after entrained liquid drops are removed, and the discharged ammonia is conveyed to an SCR denitration system after the pressure is stabilized through buffering;
the dilute ammonia water generated in the stripping process is re-atomized and then enters the ammonia stripping tower 1 again to fully release the ammonia in the ammonia water;
the dilute ammonia water reaching the discharge concentration is discharged.
Specifically, the concentration of the concentrated ammonia water is 5-30%.
Wherein when the concentration of the strong ammonia water is 5-8% or the concentration of the weak ammonia water after stripping is 0.1-1%, the stripping is a vacuum air stripping process, the temperature of the strong ammonia water in the vacuum air stripping process is 40-50 ℃, the temperature of the air is 60-80 ℃, the vacuum degree is 0.01-0.05 Mpa, the circulation rate is 5-20 times, and the operation air speed for removing entrained liquid drops is 6-9 m/s.
Wherein when the concentration of the strong ammonia water is 8-30% or the concentration of the diluted ammonia water after stripping is 1-3%, the stripping is a normal-pressure air stripping process, the temperature of the strong ammonia water in the normal-pressure air stripping process is 20 ℃, the temperature of the air is 50-60 ℃, the circulation ratio is 1-5 times, and the operation air speed for removing entrained liquid drops is 3-5 m/s.
The volume of the gas increases with increasing temperature and vacuum, with a consequent increase in the gas phase velocity in the column. Because the size of the demister is fixed, the speed of gas passing through the demister, i.e., the operating gas speed, changes with changes in temperature and vacuum, and the operating gas speed is a key parameter affecting the demisting efficiency. Therefore, the operating gas velocity of the demister needs to be set under the conditions of normal pressure and vacuum, and the good demisting and dewatering effects under the conditions of normal pressure and vacuum are ensured.
Wherein, dilute ammonia water reaching the discharge concentration is output to a coking plant for recycling, one path of dilute ammonia water is filtered to remove impurities and then is added with acid to adjust the pH value to 5-7, reverse osmosis is carried out through a brackish water reverse osmosis membrane, the reverse osmosis recovery rate is 60-90%, the reverse osmosis water production temperature is 50-60 ℃, reverse osmosis water production exchanges heat with concentrated ammonia water preheated to the preset temperature, the reverse osmosis water production recovers sensible heat and then is reduced to 30 ℃, meanwhile, the reverse osmosis water production utilizes the sensible heat to heat the concentrated ammonia water to 40-50 ℃, and the reverse osmosis water production and the concentrated ammonia water exchange heat and then are recycled as reclaimed water; and (4) outputting the reverse osmosis concentrated water to a residual ammonia water treatment unit in a coking plant, and recovering ammonia in the residual ammonia water for post-treatment until the ammonia reaches the standard and is discharged.
Compared with the prior art, the invention has the following beneficial effects:
1. at a certain temperature, the equilibrium partial pressure p of the solute gas in the gas phase above the solution is directly proportional to the concentration of this gas in the liquid phase. When the actual partial pressure p of the solute gas in the gas phase is lower than the equilibrium partial pressure p, the solute gas is transferred from the liquid phase to the gas phase, with the concentration in the liquid phase decreasing until a new equilibrium is formed. In the blowing process, gas is introduced into the liquid phase to make the gas and the liquid phase fully contact with each other, so that dissolved gas or volatile substances in the liquid phase pass through a gas-liquid interface and are transferred to the gas phase. In the SCR denitration process, ammonia gas must be diluted to a volume fraction of less than 5% before being injected into a flue, so that the ammonia gas is inevitably required to be diluted to a safe concentration by using air in the ammonia preparation process, but the ammonia preparation process and the ammonia dilution process are often independent. The method for preparing ammonia gas by blowing off ammonia water for the first time provides a reducing agent for the SCR denitration system, the preparation and dilution processes of ammonia gas are completed in the same equipment, the ammonia in the ammonia water is transferred to a gas phase by using an air blowing off method, the dilution is completed immediately, the volume fraction of the prepared ammonia gas is lower than 5%, the process flow is simplified, and the investment cost is reduced.
2. The blow-off belongs to the mass transfer process, and the driving force is the difference between the equilibrium partial pressure p of the solute gas in the gas phase and the actual partial pressure p of the solute gas in the gas phase. The vacuum degree in the stripping equipment is improved, and the actual partial pressure of ammonia gas in the gas phase can be reduced. The lower the ammonia water concentration is, the smaller the corresponding ammonia equilibrium partial pressure p is, the vacuum degree is improved, so that enough mass transfer driving force can be ensured, and the stripping effect is ensured. In addition, the solubility of ammonia in water decreases with increasing temperature at a certain pressure, and increasing temperature is also advantageous for stripping. The technological parameters of the air stripping process, such as operating temperature, vacuum and the like, are set, so that the ammonia gas can be fully released, and meanwhile, a large amount of water is prevented from being evaporated, so that the system is suitable for low-concentration ammonia water. The invention sets a reasonable control mode, sets process operation parameters such as temperature, vacuum degree and circulation rate of the system, ensures the full release of ammonia gas, and ensures that the system can use ammonia water with the concentration of 5-30% as raw materials.
3. The ammonia gas is prepared below the boiling point temperature of water, so that a large amount of evaporation of water is avoided, the energy consumption cost for ammonia preparation is reduced, the system is provided with the two-stage demister, the operating speed of the demister is set, good demisting and dewatering effects are guaranteed to be kept under normal pressure and vacuum conditions, the adverse effects of water on low-temperature catalysts and the temperature of flue gas are reduced to the maximum degree, and compared with a method for preparing ammonia gas by evaporating ammonia water, the system has good applicability to low-temperature denitration.
4. The method fully combines the existing process of the coking plant, realizes the effective utilization of resources, reduces the emission of pollutants to the maximum extent, and enters a circulating ammonia water using unit in the coking plant for recycling when the concentration of the emitted ammonia water is 1-3%; when the discharge concentration is 0.1-1%, most of water is recycled through the reverse osmosis system, most of heat is recycled through the energy saver, and only a small amount of concentrated solution is conveyed to the residual ammonia water treatment unit in the coking plant, so that the energy-saving and environment-friendly effects are achieved, and the energy-saving and environment-friendly effects are achieved.
For a better understanding of the present invention, specific examples are provided below:
the first embodiment is as follows:
in the embodiment of the invention, concentrated ammonia water with the mass concentration of 12-15% provided by a coking plant is stored in a concentrated ammonia water storage tank 2, is conveyed by a concentrated ammonia water conveying pump 3 to sequentially pass through an energy saver 4 and a concentrated ammonia water preheater 5, is preheated to 50 ℃, is conveyed to a nozzle 103, is atomized and sprayed into an ammonia gas stripping tower 1; the flow of the strong ammonia water is calculated by an ammonia water ammonia making system control module 17 according to the ammonia consumption amount and the concentrations of the strong ammonia water and the weak ammonia water which are obtained from an SCR denitration system control module 18, and the flow of the strong ammonia water is adjusted by controlling the opening of a strong ammonia water adjusting valve 1702; the dilution fan 6 conveys air to an air preheater 7, and the air enters the ammonia stripping tower 1 through an inlet between a filler layer 104 and a tower kettle 105 after being preheated to 70 ℃; the air flow is calculated by an ammonia water ammonia making system control module 17 according to the ammonia consumption of the SCR denitration system control module 18 and the concentration of the diluted ammonia gas, specifically, the volume fraction of the concentration of the diluted ammonia gas is not higher than 5%, and the air flow is adjusted by controlling the opening degree of an air adjusting valve 1706; adjusting the vacuum degree in the ammonia stripping tower 1 to be 0.05MPa through a variable-frequency adjustment ammonia draught fan 10; the ammonia water and the air are in countercurrent contact in the packing layer 104, the air continuously takes the ammonia gas in the gas phase out of the ammonia gas stripping tower 1, the gas-liquid balance of the ammonia gas is destroyed, and the ammonia gas in the ammonia water is continuously transferred to the gas phase.
The ammonia gas transferred to the gas phase is diluted by the air for stripping until the volume fraction is not higher than 5%, the diluted ammonia gas passes through the baffle plate demister 102 and the wire mesh demister 101 at the speed of 9m/s, is discharged from the top of the ammonia stripping tower 1 after entrained liquid drops are removed, enters an ammonia buffer tank 9, and is conveyed to an SCR denitration system through an ammonia draft fan 10 after the pressure is stabilized.
Dilute ammonia water generated in the stripping process is stored in a tower kettle 105, continuously circulates to a nozzle 103 under the action of an ammonia water circulating pump 8, and enters the ammonia stripping tower 1 again after being re-atomized; according to the concentration of the discharged dilute ammonia water, the ammonia water circulating pump 8 is adjusted through frequency conversion, the circulation multiplying power is adjusted to be 10 times, and the ammonia gas in the ammonia water is fully released.
The concentration of dilute ammonia water discharged by an ammonia water ammonia preparation system is 0.2%, the pH is adjusted to 5-6 by adding HCl, the dilute ammonia water is conveyed to a multi-medium multi-filter 12 and a cartridge filter 13 by a dilute ammonia water return pump 11, impurities are removed, the dilute ammonia water is conveyed to a reverse osmosis device 15 by a reverse osmosis booster pump 14, the recovery rate of the reverse osmosis device is more than or equal to 80%, and the temperature of produced water is about 60 ℃. The produced water is cooled to about 30 ℃ after sensible heat is recovered by the energy saver 4, and simultaneously, the sensible heat is utilized to heat the concentrated ammonia water provided by the coking plant to 40 ℃, and the concentrated ammonia water is recycled as reclaimed water. A small amount of reverse osmosis concentrated water is conveyed to a residual ammonia water treatment unit in a coking plant by a concentrated liquid discharge pump 16, and ammonia in the concentrated water is recovered and treated until reaching the standard for discharge.
Example two:
the process flow and the control method of the embodiment are basically the same as those of the first embodiment, except that:
the strong ammonia water with the mass concentration of 12-15% provided by the coking plant does not need to be preheated, and the air is preheated to 50 ℃. The pressure in the ammonia stripping tower 1 is normal pressure. The diluted ammonia gas passes through the baffle plate demister 102 and the wire mesh demister 101 at a speed of 3.5m/s in sequence, entrained liquid drops are removed, the ammonia gas is discharged out of the ammonia gas stripping tower, enters the ammonia gas buffer tank 9, and is conveyed to the SCR denitration system through the ammonia gas induced draft fan 10 after the pressure is stabilized. The circulation rate of the system is 3 times. The concentration of the dilute ammonia water discharged by the ammonia water system is 2%, and the dilute ammonia water is returned to the pump 11 and conveyed to the circulating ammonia water using unit in the coking plant for recycling, such as being used as a cooling medium of a cold drum section.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The utility model provides an aqueous ammonia system for denitration of coke oven flue gas which characterized in that includes:
the ammonia stripping tower (1) comprises a tower body, a demister, a nozzle (103), a filler layer (104), a tower kettle (105) and an air inlet, wherein the demister, the nozzle (103), the filler layer (104) and the tower kettle (105) are sequentially arranged in the tower body from top to bottom, and the air inlet is arranged between the tower kettle (105) and the filler layer (104);
the ammonia water conveying system comprises a concentrated ammonia water storage tank (2), a concentrated ammonia water conveying pump (3) and a concentrated ammonia water preheating device, wherein the concentrated ammonia water preheating device is communicated with the nozzle (103) and the concentrated ammonia water conveying pump (3), and the concentrated ammonia water conveying pump (3) is communicated with the concentrated ammonia water storage tank (2);
an air delivery system comprising a dilution fan (6) and an air preheater (7), the air preheater (7) being in communication with the dilution fan (6) and the air inlet;
the ammonia gas discharge system is communicated with the ammonia gas stripping tower (1);
the ammonia water circulating pump (8) is communicated with the tower kettle (105) and the nozzle (103);
ammonia water discharge system, including diluted aqueous ammonia return pump (11), filter, reverse osmosis system and dense liquid discharge pump (16), dense liquid discharge pump (16) with reverse osmosis system intercommunication, reverse osmosis system with economizer (4) with the filter intercommunication, the filter with diluted aqueous ammonia return pump (11) intercommunication, diluted aqueous ammonia return pump (11) with tower cauldron (105) intercommunication.
2. The ammonia water ammonia production system for denitration of coke oven flue gas as claimed in claim 1, wherein the demister comprises a wire mesh demister (101) and a baffle plate demister (102), and the wire mesh demister (101) and the baffle plate demister (102) are sequentially arranged in the tower body from top to bottom.
3. The ammonia water production system for denitration of coke oven flue gas as claimed in claim 1, wherein said concentrated ammonia water preheating device comprises an economizer (4) and a concentrated ammonia water preheater (5), said concentrated ammonia water preheater (5) is communicated with said nozzle (103) and said economizer (4), said economizer (4) is communicated with said concentrated ammonia water delivery pump (3).
4. The ammonia water ammonia production system for denitration of coke oven flue gas as claimed in claim 1, wherein the ammonia gas discharge system comprises an ammonia gas buffer tank (9) and an ammonia gas induced draft fan (10), the ammonia gas induced draft fan (10) is communicated with the ammonia gas buffer tank (9), and the ammonia gas buffer tank (9) is communicated with the ammonia gas stripping tower (1).
5. The ammonia-water ammonia production system for denitration of coke oven flue gas according to claim 2, wherein the reverse osmosis system comprises a reverse osmosis booster pump (14) and a reverse osmosis device (15), the reverse osmosis device (15) is communicated with the economizer (4) and the reverse osmosis booster pump (14), and the reverse osmosis booster pump (14) is communicated with the filter.
6. The ammonia-water system for denitration of coke oven flue gas according to claim 1, wherein the filter comprises a multimedia filter (12) and a cartridge filter (13), the cartridge filter (13) is communicated with the reverse osmosis system and the multimedia filter (12), and the multimedia filter (12) is communicated with the dilute ammonia water return pump (11).
7. The method for preparing ammonia from ammonia water for denitration of coke oven flue gas based on any one of claims 1 to 6 is characterized by comprising the following steps:
preheating concentrated ammonia water to a preset temperature, atomizing the preheated concentrated ammonia water, and spraying the atomized concentrated ammonia water into the ammonia stripping tower (1);
the air is preheated to a preset temperature, and the preheated air enters the ammonia stripping tower (1);
the atomized ammonia water and air are in countercurrent contact in the ammonia gas stripping tower (1) for stripping, so that ammonia in the ammonia water is continuously transferred to a gas phase to become ammonia gas, and the volume fraction of the ammonia gas is diluted to be less than or equal to 5% by the air;
the ammonia diluted by air is discharged from the top of the ammonia stripping tower (1) after entrained liquid drops are removed, and the discharged ammonia is buffered to stabilize pressure and then is conveyed to an SCR denitration system;
the dilute ammonia water generated in the stripping process is re-atomized and then enters the ammonia stripping tower (1) again to fully release the ammonia in the ammonia water;
the dilute ammonia water reaching the discharge concentration is discharged.
8. The ammonia water-ammonia production method for denitration of coke oven flue gas of claim 7, wherein when the concentration of the concentrated ammonia water is 5-8% or when the concentration of the diluted ammonia water after stripping is 0.1-1%, the stripping is a vacuum air stripping process, the temperature of the concentrated ammonia water in the vacuum air stripping process is 40-50 ℃, the temperature of the air is 60-80 ℃, the degree of vacuum is 0.01-0.05 MPa, the circulation rate is 5-20 times, and the operation gas velocity for removing entrained liquid drops is 6-9 m/s.
9. The ammonia water-ammonia production method for denitration of coke oven flue gas of claim 7, wherein when the concentration of the concentrated ammonia water is 8-30% or when the concentration of the diluted ammonia water after stripping is 1-3%, the stripping is a normal pressure air stripping process, the temperature of the concentrated ammonia water in the normal pressure air stripping process is 20 ℃, the temperature of the air is 50-60 ℃, the circulation rate is 1-5 times, and the operation air speed for removing the entrained liquid drops is 3-5 m/s.
10. The ammonia water-ammonia production method for denitration of coke oven flue gas as claimed in claim 7, wherein dilute ammonia water reaching the emission concentration is output to a coking plant for recycling, and the other path is filtered to remove impurities and then is added with acid to adjust the pH value to 5-7, and is subjected to reverse osmosis through a brackish water reverse osmosis membrane, wherein the reverse osmosis recovery rate is 60-90%, the reverse osmosis water production temperature is 50-60 ℃, the reverse osmosis water production is subjected to heat exchange with concentrated ammonia water preheated to the preset temperature, the reverse osmosis water production sensible heat is recovered and then is reduced to 30 ℃, meanwhile, the reverse osmosis water production heats the concentrated ammonia water to 40-50 ℃ by utilizing the sensible heat, and the reverse osmosis water production and the concentrated ammonia water are recycled as reclaimed water after heat exchange; and (4) outputting the reverse osmosis concentrated water to a residual ammonia water treatment unit in a coking plant, and recovering ammonia in the residual ammonia water for post-treatment until the ammonia reaches the standard and is discharged.
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