CN114534478A - Ammonia desulphurization system and operation method thereof - Google Patents

Ammonia desulphurization system and operation method thereof Download PDF

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Publication number
CN114534478A
CN114534478A CN202210175019.4A CN202210175019A CN114534478A CN 114534478 A CN114534478 A CN 114534478A CN 202210175019 A CN202210175019 A CN 202210175019A CN 114534478 A CN114534478 A CN 114534478A
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China
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heat
ammonia
flue gas
heat pump
liquid
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CN202210175019.4A
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Chinese (zh)
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张军
罗静
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Jiangsu New Century Jiangnan Environmental Protection Co ltd
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Jiangsu New Century Jiangnan Environmental Protection Co ltd
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Priority to CN202210175019.4A priority Critical patent/CN114534478A/en
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • B01D47/06—Spray cleaning
    • 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
    • B01D53/343—Heat recovery
    • 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
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B27/00—Machines, plants or systems, using particular sources of energy
    • F25B27/02—Machines, plants or systems, using particular sources of energy using waste heat, e.g. from internal-combustion engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B30/00—Heat pumps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/27—Relating to heating, ventilation or air conditioning [HVAC] technologies
    • Y02A30/274—Relating to heating, ventilation or air conditioning [HVAC] technologies using waste energy, e.g. from internal combustion engine

Abstract

The invention relates to an ammonia desulphurization system and an operation method thereof, wherein the ammonia desulphurization system comprises an ammonia desulphurization device (1) which is configured to remove SO in flue gas2The ammonia desulfurization apparatus has a solution circulation having a circulation line configured to circulate a solution in direct contact with the flue gas in the ammonia desulfurization apparatus, and the ammonia desulfurization system further includes a heat pump (11a, 11b, 11c) having a heat source connected to the heat pumpThe inlet and the heat source outlet are connected, and the heat pump is configured to extract heat from the circulating liquid in the circulating line as the heat source. Through this kind of ammonia process desulfurization system, can realize ammonia process desulfurization's waste heat recovery and condensate water recovery and ammonia escape and the control of tiny particle emission.

Description

Ammonia desulphurization system and operation method thereof
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to an ammonia desulphurization system and a method for operating the ammonia desulphurization system, so that waste heat recovery and condensate water recovery of ammonia desulphurization, ammonia escape and fine particulate matter emission control can be realized.
Background
At present, the mainstream process for removing sulfur dioxide from gas on a global scale comprises a limestone-gypsum method, which generates a large amount of wastewater and gypsum slag during the desulfurization process, wherein 0.7 ton of carbon dioxide is synchronously generated for every 1 ton of sulfur dioxide removal. The treatment of such waste water and slag requires a large amount of investment and running costs. Compared with calcium desulphurization, ammonia desulphurization can basically not generate wastewater and waste residue, and the added desulfurizer ammonia can be converted into ammonium sulfate fertilizer, thereby changing waste into valuable. Typically, the sales revenue of ammonium sulfate fertilizers can be greater than the input cost of ammonia.
In the ammonia desulphurization process, the absorption circulating liquid and the fine particle washing circulating liquid can be collected by corresponding gas-liquid separators and flow back to respective circulating tanks, then the circulating liquid can be pumped out from the circulating tanks by circulating pumps, pressurized and sent to corresponding spraying layers, and dispersed by nozzles of the spraying layers and then contacted with flue gas. The ammonia desulfurization device generally comprises a cooling function area, an absorption function area and a fine particle control function area. Absorbent ammonia, such as simple substance ammonia, ammonia water or ammonium bicarbonate, can be added into the circulating liquid in the absorption functional zone, and the absorption liquid with ammonia can absorb SO in the flue gas flowing through the absorption functional zone2At this time, ammonia in the absorption liquid may be volatilized into the gas phase, which may cause ammonia to slip. The inventors of the present application have found in research and development of products that low absorption liquid temperatures can reduce ammonia partial pressure and aerosol, thereby reducing ammonia slip and particulate matter.
The exhaust flue gas temperature of ammonia desulfurization generally exceeds 50 ℃, and therefore, a large amount of heat is released in the form of latent heat of vaporization of water vapor. The inventor of the application finds that in ammonia desulphurization, if the absorption circulating liquid is cooled by arranging a heat exchanger in the absorption circulating liquid, the cooled absorption circulating liquid is contacted with the flue gas to remove heat in the flue gas and reduce the temperature of the flue gas, but a large amount of cold sources such as circulating cooling water are consumed, and the operation cost is increased. In addition, the temperature of the flue gas at the tail part of the boiler is low, and the temperature of the outlet water is difficult to be continuously increased.
CN111457408A discloses a flue gas rotational flow injection de-whitening coupling absorption heat pump waste heat recovery device and method, the device includes a desulfurizing tower, a fan, a rotational flow ejector, an alkali liquor tank, a liquor collecting tank, a water storage tank, an absorption heat pump and a driving heat source, wherein the rotational flow ejector cuts and atomizes liquid into small drops, heat transfer and mass transfer coefficients of flue gas and the drops are increased, the drops become low-temperature heat source water after absorbing flue gas heat, the drops flow into the absorption heat pump to release heat and cool to become cooling water, one part of the cooling water is used for supplementing water for slurry of the desulfurizing tower, the other part of the cooling water enters the rotational flow ejector, and the atomized cooling water absorbs the flue gas heat. The cyclone injector is required to be arranged independently, atomized liquid drops transfer heat in the flue gas to atomized water, and then the atomized water is used as low-temperature heat source water of the heat pump.
CN109045976A discloses an ammonia process desulfurization flue gas white elimination and waste heat degree of depth recovery system, the system includes desulfurizing tower, circulating water tank, heat exchanger, absorption heat pump, flue gas cooling section, flue gas section of heating, heat exchanger, absorption heat pump can carry out two-stage cooling to the circulating water, carry out two-stage heating to the boiler moisturizing simultaneously. In the prior art, only the waste heat recovery and the white elimination in the flue gas are taken into account, and the problem of ammonia escape control in the ammonia desulphurization process is not solved. In addition, the prior art is combined with a boiler process, and the modification difficulty and the modification equipment amount are large. In addition, the high-quality steam of the boiler is utilized to recover low-level heat energy, so that the effective energy efficiency is low; for the rewarming of the discharged flue gas, heat pipe heat exchange equipment is used, which is high in investment.
CN113144875A discloses a waste heat utilization device suitable for wet desulphurization of flue gas of a heating boiler, which comprises a slurry circulating pump and a slurry cooler connected in parallel with a desulphurization tower and connected in sequence. The slurry cooler is connected with the spraying layer and is connected with the steam source heat pump in parallel. In this prior art, the slurry needs to be cooled by circulating water, and the cooling water then enters the heat pump as a low-temperature heat source to be recovered with waste heat. In this case, a heat exchanger needs to be added, so that the heat exchange efficiency is greatly reduced, and the grade of the recovered heat is also reduced. This prior art only focuses on waste heat recovery of the flue gas.
CN211177999U discloses a flue gas water heat recycling system, in which a heat pump is used to reduce the temperature of flue gas so as to achieve the purpose of water heat recycling. In this system, the flow is complicated, wherein, uses indirect heating equipment to carry out a lot of cooling to the flue gas, and this investment is big and later stage operation maintenance cost is high.
CN112023639A discloses a latent heat recycling device and method for flue gas treatment in coal-fired power plants, wherein the flue gas is cooled by waste heat recovery before entering a desulfurizing tower, and the flue gas after entering the desulfurizing tower is cooled by a heat exchanger to recover condensate in the flue gas.
Disclosure of Invention
It is an object of the present invention to provide an ammonia desulfurization system and a method for operating an ammonia desulfurization system, by which waste heat recovery and condensate recovery of ammonia desulfurization and control of ammonia slip and fine particulate matter emission can be achieved.
A first aspect of the invention relates to an ammonia desulfurization system comprising an ammonia desulfurization unit configured to remove SO from flue gas2The ammonia desulfurization apparatus has a solution circulation having a circulation line configured to circulate a solution in the ammonia desulfurization apparatus, which is in direct contact with the flue gas, wherein the ammonia desulfurization system further includes a heat pump connected to a heat source inlet and a heat source outlet of the heat pump, the heat pump being configured to extract heat from a circulation liquid in the circulation line as a heat source.
By recovering waste heat from the solution of the ammonia desulphurization device, through which the flue gas flows, by using the heat pump, the temperature of the solution can be reduced, which can reduce the temperature of the flue gas flowing through, which can help to control ammonia escape and aerosol generation, help to control fine particulate matter emission, and is beneficial to recovering condensed water from the flue gas or reducing moisture in the outlet flue gas.
In some embodiments, the solution circulation may have a circulation pump disposed in the circulation line. The heat pump may be downstream of the circulation pump. Alternatively, the heat pump may be upstream of the circulation pump.
In some embodiments, a solid-liquid separation device for separating solid impurities in the solution may be provided in the circulation line, upstream of the heat pump. Through the solid-liquid separation device, solid impurities can be prevented from entering the heat pump, scaling in the heat pump can be prevented, the heat pump is blocked, and the working performance of the heat pump is prevented from being influenced. The separated solid particles may be sent to an ammonium sulfate post-treatment system. The solid-liquid separation apparatus may be, for example, a filter press.
In some embodiments, the ammonia desulfurization device may include a cooling function zone, an absorption function zone and a fine particulate matter control function zone, wherein the cooling function zone has a function for removing SO to be removed2The flue gas is input into a flue gas inlet of the ammonia desulphurization device, the cooling functional area is configured to cool the flue gas flowing through, and the absorption functional area is configured to absorb SO from the flue gas flowing through by absorption liquid containing ammonia absorbent2The fine particle control function is configured to remove fine particles from flue gas flowing therethrough with a scrubbing liquid.
In some embodiments, the absorption function zone may be provided with an absorption liquid circulation having an absorption liquid circulation line.
In some embodiments, the absorption liquid circulation line may be connected to a heat source inlet and a heat source outlet of a first heat pump configured to extract heat from the absorption liquid in the absorption liquid circulation line as a heat source.
In some embodiments, the fine particle control function may be provided with a wash liquor circulation having a wash liquor circulation line connected to a heat source inlet and a heat source outlet of a second heat pump provided and configured to extract heat from the wash liquor circulation in the wash liquor circulation line as a heat source.
In some embodiments, the fine particulate control function zone may be provided with first and second scrubbing liquid circulation in sequence along the flow direction of the flue gas.
In some embodiments, the first and second wash liquor cycles can be configured such that the first wash liquor cycle operating in the first wash liquor cycle has a higher ammonium sulfate concentration than the second wash liquor cycle operating in the second wash liquor cycle.
In some embodiments, the first and second wash liquor cycles can be configured such that the first wash liquor cycle operating in the first wash liquor cycle has a concentration of ammonium sulfate in the range of 50 to 400g/L, preferably 100 to 350g/L, such as 150 to 300g/L, and/or the second wash liquor cycle operating in the second wash liquor cycle has a concentration of ammonium sulfate in the range of 0 to 80g/L, such as 0 to 50g/L, preferably 0 to 20 g/L.
In some embodiments, each solution cycle of the ammonia desulfurization unit may have one or more spray levels through which the respective circulating liquid can be returned to the respective functional zone of the ammonia desulfurization unit.
In some embodiments, each two adjacent functional zones of an ammonia desulfurization unit may be divided by a gas-liquid separator that allows only gas to pass through.
In some embodiments, the first scrubbing liquid circuit can be provided with a second heat pump for extracting heat from the first scrubbing liquid in the first scrubbing liquid circuit as a heat source.
In some embodiments, the second scrubbing liquid circuit can be provided with a second heat pump for extracting heat from the second scrubbing liquid in the second scrubbing liquid circuit as a heat source.
In some embodiments, the first and second scrubbing liquid circuits can each be provided with a second heat pump for extracting heat from the respective scrubbing liquid in the respective scrubbing liquid circuit as a heat source.
In some embodiments, the first and second scrubbing liquid circuits can be provided with a common second heat pump for extracting heat from the first scrubbing liquid circuit in the first scrubbing liquid circuit as a heat source and for extracting heat from the second scrubbing liquid circuit in the second scrubbing liquid circuit as a heat source.
In some embodiments, the heat pump may be a compression heat pump or an absorption heat pump.
In some embodiments, the heat pump may be an electrically driven compression heat pump.
In some embodiments, the heat pump may be a gas-driven, steam-driven, or hot water-driven absorption heat pump.
In some embodiments, lithium bromide may be employed as an absorbent in an absorption heat pump.
In some embodiments, in the absorption heat pump, water may be used as a refrigerant of the absorption heat pump, and the absorbent may be dissolved in the refrigerant.
In some embodiments, the parts of the heat pump that contact the circulating liquid may be made of corrosion-resistant materials, such as 316L, 2205, 2507 steel, or titanium, etc.
In some embodiments, the flue gas outlet of the ammonia desulfurization unit may be equipped with a heat exchange device configured to heat the outlet flue gas.
In some embodiments, the heat exchange device may be thermally connected to a heat pump, such that the heat of the heat exchange device for heating the outlet flue gas can partly or completely come from the heat pump.
In some embodiments, the working fluid of the heat exchange device for heating the outlet flue gas may be selected from the group consisting of air, steam and process recycle water.
In some embodiments, the ammonia desulfurization system may be configured such that the waste heat recovered by the heat pump is used to heat any one or any combination of the power plant condensate, boiler feed water, outlet flue gas of the ammonia desulfurization plant, and hot supply water.
A second aspect of the invention relates to a method for operating an ammonia desulfurization system, wherein waste heat recovery and condensate recovery are achieved and ammonia slip and fine particulate emissions are controlled, the method comprising:
operating an ammonia desulfurization plant wherein SO is to be contained2The flue gas is conveyed to an ammonia desulphurization device, and SO in the flue gas is removed by using absorption liquid containing ammonia desulfurizer2(ii) a And is
Operating the heat pump to extract heat from the circulating liquid in the circulating line as a heat source;
wherein, realize waste heat recovery through the heat pump, reduce the temperature with the solution of flue gas direct contact among the ammonia process desulphurization unit, reduce ammonia escape and tiny particulate matter and discharge to and realize the comdenstion water recovery.
In some embodiments, the first heat pump may be operated to lower the temperature of the absorption liquid to reduce the ammonia concentration and aerosol generation in the absorption function.
In some embodiments, a second heat pump associated with the fine particle control function may be operated to reduce the temperature of the scrubbing liquid to condense water vapor in the flue gas in the fine particle control function and to reduce the entrainment of fine particles in the flue gas in the fine particle control function.
In some embodiments, the ammonia desulfurization system may be operated such that: the temperature of the circulating liquid of the heat inlet pump as a heat source is controlled to be 20-70 ℃, and preferably 40-60 ℃; and/or controlling the temperature of the circulating liquid of the heat pump to be 10-60 ℃, preferably 20-50 ℃; and/or controlling the temperature of the flue gas of a functional area of the ammonia desulphurization device, which is connected with the heat pump, to be 20-70 ℃, preferably 40-60 ℃.
In some embodiments, the heat exchange device can be operated so that the outlet flue gas temperature after heat exchange is controlled to be 30-60 ℃, preferably 35-50 ℃.
In some embodiments, the benefits of the present invention may be: the waste heat and the condensate water in the flue gas desulfurized by the ammonia method are recycled, and meanwhile, the desulfurization temperature is controlled, the volatilization of ammonia into a gas phase in the desulfurization absorption liquid is reduced, the ammonia escape is reduced, and the generation of fine particles is reduced. The heat pump technology and the desulphurization device are highly integrated, the equipment investment is low, and the aims of environmental protection and energy conservation can be further fulfilled efficiently.
The features already mentioned above, those to be mentioned below and those shown in the figures individually can be combined with one another as desired, provided that the combined features are not mutually inconsistent. All possible combinations of features are the subject matter of the technology explicitly described herein. Any of a plurality of sub-features included in the same sentence may be applied independently, not necessarily together with other sub-features.
Drawings
Exemplary embodiments of the ammonia desulfurization system according to the present invention are described below with reference to the schematic drawings. In the drawings:
FIG. 1 is a schematic diagram of an ammonia desulfurization system according to a first embodiment of the present invention.
FIG. 2 is a schematic diagram of an ammonia desulfurization system in accordance with a second embodiment of the present invention.
FIG. 3 is a schematic diagram of an ammonia desulfurization system as a comparative example.
Detailed Description
First, an ammonia desulfurization system 100 according to a first embodiment of the present invention will be described with reference to fig. 1. The ammonia desulfurization system 100 includes an ammonia desulfurization unit 1 configured to remove SO from flue gas2. In the embodiment shown in fig. 1, the ammonia desulfurization apparatus 1 is configured as an ammonia desulfurization tower including three functional zones, i.e., a cool-down functional zone 3, an absorption functional zone 4, and a fine particulate matter control functional zone 5, which are arranged in this order from bottom to top.
In a not shown embodiment, any one of the functional zones can be designed as a single unit or any two of the functional zones can be integrated into a single unit, for example three functional zones can each be designed as a single column, which columns are connected via lines. In a not shown embodiment, not only the three functional zones described above can be integrated in one and the same device, but additionally also a further functional zone, for example an oxidation functional zone, in which the oxidation of the absorption liquid can be carried out with compressed air.
The cooling function area 3 is provided with a cooling function area for coolingTo be deprived of SO2The flue gas is input into a flue gas inlet 2 of the ammonia desulphurization device. The cooling functional area 3 is constructed to be used for cooling the flue gas that flows through, and when the flue gas cooling, the heat of flue gas is used for carrying out evaporative concentration to the ammonium sulfate solution or the ammonium sulfate thick liquid that hold in the cooling functional area 3. The cooling function zone 3 may be provided with a circulation pump and a circulation line for an ammonium sulfate solution or an ammonium sulfate slurry, not shown. The ammonium sulfate solution or ammonium sulfate slurry reaching the predetermined concentration in the cooling and temperature-lowering functional region 3 can be output to an ammonium sulfate post-treatment system and can be finally processed into an ammonium sulfate fertilizer. The flow of flue gas in the ammonia desulfurization unit 1 is schematically represented in fig. 1 by three arrows p1, p2, p 3.
The cool-down function zone 3 and the absorption function zone 4 may be divided by a gas-liquid separator 6a that allows only gas to pass therethrough. The flue gas may flow from the cool-down function zone 3 into the absorption function zone 4 via the gas-liquid separator 6a after cooling down. The absorption function 4 is designed to absorb SO from flue gas flowing through it with an absorption liquid containing an ammonia absorbent2. The absorption function zone 4 may be provided with an absorption liquid circulation 21 having an absorption liquid circulation line. The absorption liquid collected on the gas-liquid separator 6a can be transported by gravity through a pipe section to the absorption liquid circulation tank 9. The absorption liquid contained in the absorption liquid circulation tank 9 can be returned to the absorption function region 4 via an absorption liquid circulation pump 10 via further pipe sections, for example, can be sprayed into the absorption function region 4 in a counter-current manner with the flue gas via a single absorption stage spray layer 7 (or alternatively via a plurality of absorption stage spray layers), and is brought into direct contact with the flue gas flowing through, SO in the flue gas flowing through is absorbed by the ammonia absorbent in the absorption liquid2. The absorption liquid cycle 21 may be provided with a first heat pump 11 a. Specifically, the absorption liquid circulation line may be connected to a heat source inlet and a heat source outlet of the first heat pump 11a, the first heat pump 11a being configured to extract heat from the absorption circulation liquid in the absorption liquid circulation line as a heat source. The first heat pump 11a may be disposed downstream of the absorption circulation pump 10, and a solid-liquid separation device 16a, for example, a solid-liquid separation device 16a may be disposed between the absorption circulation pump 10 and the first heat pump 11aAnd (4) a filter press.
The absorption liquid circulation tank 9 can be configured as an oxidation tank for the absorption liquid, wherein oxidation air can be fed in the form of compressed air into the absorption liquid circulation tank 9 and thus the absorption liquid contained in the absorption liquid circulation tank 9 is oxidized, wherein ammonia sulfite (hydrogen) can be oxidized into ammonia sulfate (hydrogen). The absorption liquid circulation tank 9 may be connected to an ammonia adding device, not shown, which may add an ammonia absorbent to the absorption liquid. For example, an ammonia adding chamber may be provided inside the absorption liquid circulation tank 9.
By extracting heat from the absorption circulating liquid by the first heat pump 11a, recovery of waste heat of ammonia desulfurization can be achieved, the absorption liquid having a reduced temperature can be achieved, and thereby the flue gas directly contacting the absorption liquid can have a reduced temperature, which can reduce the partial pressure of ammonia and aerosol in the gas phase in the absorption functional zone 4, thereby reducing ammonia slip. In addition, the flue gas leaving the absorption function 4 and reaching the fine particle control function 5 at a reduced temperature is also improved in terms of fine particle emissions and the moisture in the outlet flue gas is also reduced.
The absorption function zone 4 and the fine particulate matter control function zone 5 may be divided by a gas-liquid separator 6b that allows only gas to pass therethrough. The flue gas may flow from the absorption function zone 4 into the fine particulate control function zone 5 via the gas-liquid separator 6 b. The fine particle control function 5 is configured to remove fine particles from flue gas flowing therethrough with scrubbing liquid. The fine particle control function 5 can be provided with a washing liquid circulation 22 having a washing liquid circulation line. The scrubbing liquid collected on the gas-liquid separator 6b can be run in the scrubbing liquid circulation line by the scrubbing liquid circulation pump 12 and returned again into the fine particulate matter control function zone 5. If necessary, a not shown scrubbing liquid circulation tank can be provided, into which the scrubbing liquid collected in the gas-liquid separator 6b can be conveyed by gravity via a pipe section and then returned from there via a scrubbing liquid circulation pump 12 via further pipe sections into the fine-particle control function 5, for example by means of a single spray layer 8 (or alternatively by means of a plurality of such spray layers) in countercurrent to the flue gas, into the fine-particle control function 5, in direct contact with the flue gas flowing past, for scrubbing off the fine particles entrained in the flue gas. The washing liquid circulation 22 may be provided with a second heat pump 11 b. Specifically, the washing liquid circulation line may be connected with a heat source inlet and a heat source outlet of the second heat pump 11b, the second heat pump 11b being configured to extract heat from the washing circulation liquid in the washing liquid circulation line as a heat source.
By extracting heat from the scrubbing circulation liquid using the second heat pump 11b, the scrubbing liquid can have a reduced temperature, which can cause the flue gas flowing through the fine particle control function 5 to have a reduced temperature. This may reduce fine particulate matter entrained by the flue gas and may facilitate recovery of condensed water from the flue gas, so that the flue gas exiting the flue gas outlet may have a reduced fine particulate matter content as well as moisture.
Above the fine particulate control function zone 5, the ammonia desulfurization device 1 may have a flue gas outlet, which may be equipped with a heat exchange device 13 configured to heat the outlet flue gas, achieving a flue gas whitening effect. Said heat exchanging means 13 may be thermally connected to at least one of the heat pumps 11a, 11b, e.g. only the heat pump 11b, so that the heat of the heat exchanging means 13 for heating the outlet flue gas can partly or completely come from said at least one heat pump. The working fluid of the heat exchange device 13 for heating the outlet flue gas may for example be selected from the group comprising air, steam and process circulating water.
Each of the heat pumps 11a, 11b may be a compression heat pump or an absorption heat pump, for example an electrically driven compression heat pump, or a gas driven, steam driven or hot water driven absorption heat pump. In the embodiment shown, steam is used as the driving heat source, which steam may be generated, for example, in a heat exchanger that is capable of obtaining heat from the raw flue gas before the raw flue gas is fed to the ammonia desulfurization unit 1.
The waste heat of ammonia desulfurization extracted by each heat pump can be widely used, and can be used for heating any one or any combination of multiple of power generation device condensate, boiler feed water, outlet flue gas of ammonia desulfurization device and hot water. In the illustrated embodiment, the desalinated water may be delivered to each heat pump and used as boiler feed water after being warmed by the heat pump.
In the operation of the ammonia desulfurization system 100, it is advantageous that, for each heat pump 11a, 11b, the temperature of the circulating liquid entering the heat pump as a heat source is controlled to be 20 to 70 ℃, preferably 40 to 60 ℃, and the temperature of the circulating liquid exiting the heat pump is controlled to be 10 to 60 ℃, preferably 20 to 50 ℃; the flue gas temperature of a functional area of the ammonia desulphurization device connected with the heat pump is controlled to be 20-70 ℃, and preferably 40-60 ℃; the temperature of the outlet flue gas after heat exchange is controlled to be 30-60 ℃, and preferably 35-50 ℃.
FIG. 2 is a schematic diagram of an ammonia desulfurization system 200 in accordance with a second embodiment of the present invention. The ammonia desulfurization system 200 according to the second embodiment differs from the ammonia desulfurization system 100 according to the first embodiment mainly in that the fine particulate matter control function zone 5 is provided with two scrubbing liquid circulations 22a, 22b, i.e., a first and a second scrubbing liquid circulations in this order along the flow direction of the flue gas. Next, differences between the second embodiment and the first embodiment will be mainly described. In other aspects of the second embodiment, reference may be made to the description of the first embodiment, which is not repeated here.
The first and second wash liquor circuits 22a, 22b are configured such that the first wash liquor circuit operating in the first wash liquor circuit 22a has a higher ammonium sulfate concentration than the second wash liquor circuit operating in the second wash liquor circuit 22 b. Advantageously, the first washing liquor circulation operating in the first washing liquor circuit 22a has a concentration of ammonium sulphate of 50 to 400g/L, preferably 100 to 350g/L, and the second washing liquor circulation operating in the second washing liquor circuit 22b has a concentration of ammonium sulphate of 0 to 80g/L, preferably 0 to 20 g/L.
For the first scrubbing liquid circulation 22a, a gas-liquid separator 6b that allows only gas to pass is provided, and this gas-liquid separator 6b separates the absorption function zone 4 from the fine particulate matter control function zone 5. For the second washing liquid circulation 22b, a gas-liquid separator 6c that allows only gas to pass is provided in the fine particulate matter control function region 5, and this gas-liquid separator 6c divides the fine particulate matter control function region 5 into two sub-regions 5a, 5 b. The first washing liquid circuit 22a has a spray layer 8a in the first sub-zone 5a and a first washing liquid circulation pump 12a, and is provided with a second heat pump 11b for extracting heat from the first washing liquid circulation in the first washing liquid circulation line as a heat source, and a solid-liquid separation device 16b is provided between the first washing liquid circulation pump 12a and the second heat pump 11 b. The second washing liquid circulation 22b has a spray layer 8b in the second sub-zone 5b and a second washing liquid circulation pump 12b, and a second heat pump 11c for extracting heat from the second washing liquid circulation in the second washing liquid circulation line as a heat source is arranged, and a solid-liquid separation device 16c is provided between the second washing liquid circulation pump 12b and the second heat pump 11 c. At least one of the heat pumps 11a, 11b, 11c may provide heat to the heat exchanger 13 to heat the outlet flue gas. For the sake of simplicity, only the connection of the second heat pump 11c to the heat exchanger 13 is depicted in fig. 2.
In the embodiment shown in fig. 1 and 2, the cooling function zone 3 is not provided with a heat pump, and the absorption function zone 4 and the fine particulate control function zone 5 are each provided with at least one heat pump. Typically, the supercooling functional zone 3 is not provided with a heat pump, however, in principle the supercooling functional zone 3 may also be provided with a heat pump. In an embodiment not shown, one of the absorption function zone 4 and the fine particulate control function zone 5 may not be provided with a heat pump. In a not shown embodiment, the first scrubbing liquid circuit 22a and the second scrubbing liquid circuit 22b can be assigned a common second heat pump.
In the embodiment shown in fig. 1 and 2, the absorption liquid can be used as a replacement liquid for the supercooling functional zone 3, for which purpose the absorption liquid can be conducted directly or indirectly from the absorption functional zone 4 or the absorption liquid circuit into the supercooling functional zone 3 as required via a branch line, not shown. The scrubbing liquid can be used as a make-up liquid for the absorption function 4, for which purpose the scrubbing liquid can be conducted directly or indirectly from the fine-particle control function 5 or the scrubbing liquid circuit into the absorption function 4 as required via branch lines, not shown. The process water may be added directly or indirectly to the fine particle control function zone 5 as a replacement fluid for the fine particle control function zone 5.
In the exemplary application of the ammonia desulfurization system 200 shown in FIG. 2, the main design parameters of the ammonia desulfurization system 200 are as follows:
the tower diameter of the ammonia desulfurization tower is 8.5m, and the amount of flue gas to be treated is 460588Nm3The temperature of the raw flue gas is 160 ℃, the water content is 8.5 percent (volume), the oxygen content is 6 percent (volume), and the SO content is2The concentration is 2000mg/Nm3. The absorption function is provided with three spray levels (for the sake of simplicity, only one spray level 7 is depicted in fig. 2), each of which has a spray volume of 650m3And h, arranging a first heat pump at the outlet of the absorption circulating pump, and reducing the temperature of the absorption circulating liquid from 48 ℃ (in the case of the shutdown of the first heat pump) to 38 ℃ (in the case of the operation of the first heat pump). The temperature of the flue gas after being sprayed and cooled by the absorption circulating liquid is reduced to 50 ℃, and the heat of the flue gas is recovered by the first heat pump to be 7335 kW. The fine particle control function area is provided with two spraying layers, and the spraying amount of each layer is 650m3A second heat pump is provided at the outlet of each wash liquor circulation pump, reducing the wash liquor circulation temperature from 43 ℃ (in case the second heat pump is switched off) to 33 ℃ (in case the second heat pump is running). The temperature of the flue gas after being sprayed and cooled by the washing circulating liquid is reduced to 45 ℃, and the heat of the flue gas is recovered by the second heat pump to be 7310 kW. And heating the outlet flue gas to 70 ℃ by utilizing the waste heat recovered by at least one heat pump. Through calculation, the clean flue gas SO is discharged2The concentration is 15mg/Nm3Total dust 2.1mg/Nm3The escape amount of ammonia is 0.9mg/Nm3. The process water consumption was 6.3 t/h. The recovered heat was 14645 KJ.
FIG. 3 is a schematic diagram of an ammonia desulfurization system 300 as a comparative example. In the ammonia desulfurization system 300, the ammonia desulfurization apparatus is basically configured the same as the ammonia desulfurization apparatus of the ammonia desulfurization system 200 shown in fig. 2, and the description of the ammonia desulfurization apparatus of the ammonia desulfurization system 200 can be referred to. In fig. 2 and 3, the same reference numerals denote the same or similar components. The ammonia desulfurization system 300 does not include the heat pumps 11a, 11b, and 11c, the solid- liquid separation devices 16a, 16b, and 16c provided to the heat pumps, and the heat exchanger 13 for heating the outlet flue gas as in the embodiment shown in fig. 2.
In the comparative example, the design parameters of the ammonia desulfurization apparatus were the same as those of the ammonia desulfurization apparatus shown in FIG. 2. Through calculation, the temperature of the outlet flue gas is controlled to be 54 ℃, and the outlet clean flue gas SO2The concentration is 32mg/Nm3Total dust 10.5mg/Nm3The escape amount of ammonia is 5.0mg/Nm3. The process water consumption was 26.3 t/h.
The comparison shows that the implementation mode of the ammonia desulphurization system can obviously improve the environmental protection performance of ammonia desulphurization and reduce the equipment operation cost, wherein the flue gas can be subjected to gradient cooling by utilizing a heat pump technology, heat and condensate water are recovered, and waste heat recovery and water consumption reduction are realized. Here, reduce the desulfurization temperature and can reduce ammonia concentration and aerosol in the gaseous phase of absorption function district and generate, the while cooling can be with the condensation of water vapor in the fine particle control function district flue gas, reduces the fine particle that smugglies secretly in the flue gas, control ammonia escape and fine particle emission. In the embodiment of the invention, the heat pump technology can be deeply combined with the ammonia desulphurization technology, the ammonia escape and the fine particulate matter emission of the ammonia desulphurization are controlled, the low water consumption and even zero water consumption are realized, and the cascade comprehensive utilization of heat recovery is realized. In the embodiments, the invention integrates waste heat recovery, condensate recovery, ammonia escape and particulate matter emission control, and has the advantages of low operation cost, reliable performance index and the like. Unlike the embodiment according to the invention, in the prior art, the wet flue gas discharged after ammonia desulfurization still contains a large amount of heat and water vapor.
It is noted that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting of the disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be understood that the terms "comprises" and "comprising," and other similar terms, when used in this specification, specify the presence of stated operations, elements, and/or components, but do not preclude the presence or addition of one or more other operations, elements, components, and/or groups thereof. The term "and/or" as used herein includes all arbitrary combinations of one or more of the associated listed items. In the description of the drawings, like reference numerals refer to like elements throughout.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. Thus, a first element could be termed a second element without departing from the teachings of the present inventive concept.
Finally, it is pointed out that the above-described embodiments serve only for the understanding of the present application and do not limit the scope of protection of the present application. It will be apparent to those skilled in the art that modifications may be made in the above-described embodiments without departing from the scope of the application.

Claims (10)

1. An ammonia desulfurization system comprising an ammonia desulfurization unit (1) configured to remove SO from flue gas2The ammonia desulfurization plant has a solution circulation having a circulation line configured to circulate a solution in the ammonia desulfurization plant in direct contact with the flue gas, characterized in that the ammonia desulfurization system further comprises a heat pump (11a, 11b, 11c) connected to a heat source inlet and a heat source outlet of the heat pump, the heat pump being configured to extract heat from the circulating liquid in the circulation line as a heat source, preferably the heat pump is a compression heat pump or an absorption heat pump, further preferably the heat pump is an electrically driven compression heat pump, or a gas-driven, steam-driven or hot-water-driven absorption heat pump.
2. The ammonia desulfurization system according to claim 1, wherein the solution circulation has a circulation pump (10, 12a, 12b, 12c) provided in a circulation line;
preferably, in the circulation line, upstream of the heat pump, a solid-liquid separation device (16a, 16b, 16c) for separating solid impurities in the solution is provided.
3. The ammonia desulfurization system according to any one of claims 1 to 2, wherein the ammonia desulfurization device comprises a cool-down functional zone (3), an absorption functional zone (4) and a fine particulate control functional zone (5), wherein the cool-down functional zone has a function for removing SO to be removed2The flue gas is input into a flue gas inlet (2) of the ammonia desulphurization device, the cooling functional area is configured to cool the flue gas flowing through, and the absorption functional area is configured to absorb SO from the flue gas flowing through by absorption liquid containing ammonia absorbent2The fine particle control function is configured to remove fine particles from flue gas flowing therethrough with a scrubbing liquid.
4. The ammonia desulfurization system according to claim 3, wherein the absorption function zone is provided with an absorption liquid cycle (21) having an absorption liquid cycle line connected to a heat source inlet and a heat source outlet of a first heat pump configured to extract heat from the absorption cycle liquid in the absorption liquid cycle line as a heat source; and/or
The fine particle control function zone is provided with a washing liquid circulation (22, 22a, 22b) having a washing liquid circulation line connected to a heat source inlet and a heat source outlet of a second heat pump provided for extracting heat from the washing circulation liquid in the washing liquid circulation line as a heat source;
preferably, the fine particle control function is provided with a first and a second scrubbing liquid circuit in succession in the flow direction of the flue gas, the first and second scrubbing liquid circuits being configured such that the first scrubbing liquid circulating in the first scrubbing liquid circuit has a higher ammonium sulfate concentration than the second scrubbing liquid circulating in the second scrubbing liquid circuit;
further preferably, the first and second wash liquor circuits are configured such that the first wash liquor circuit operating in the first wash liquor circuit has a concentration of 50 to 400g/L, preferably 100 to 350g/L, of ammonium sulphate and the second wash liquor circuit operating in the second wash liquor circuit has a concentration of 0 to 80g/L, preferably 0 to 20g/L, of ammonium sulphate.
5. The ammonia desulfurization system according to any one of claims 1 to 4,
the first scrubbing liquid circuit is provided with a second heat pump for extracting heat from the first scrubbing liquid circulating in the first scrubbing liquid circuit as a heat source; or
The second scrubbing liquid circuit is provided with a second heat pump for extracting heat from the second scrubbing liquid circulating in the second scrubbing liquid circuit as a heat source; or
The first and second scrubbing liquid circuits are each associated with a second heat pump for extracting heat from the respective scrubbing liquid in the respective scrubbing liquid circuit as a heat source; or
The first and second scrubbing liquid circuits are associated with a common second heat pump for extracting heat from the first scrubbing liquid circulating in the first scrubbing liquid circuit as a heat source and for extracting heat from the second scrubbing liquid circulating in the second scrubbing liquid circuit as a heat source.
6. The ammonia desulfurization system according to any one of claims 1 to 5, characterized in that the flue gas outlet of the ammonia desulfurization device is equipped with a heat exchange device (13) configured for heating the outlet flue gas;
preferably, the heat exchange device is thermally connected with the heat pump, so that the heat of the heat exchange device for heating the outlet flue gas can partially or completely come from the heat pump;
preferably, the working medium of the heat exchange device for heating the outlet flue gas is selected from the group consisting of air, steam and process circulating water;
and/or the ammonia desulphurization system is constructed in a way that the waste heat recovered by the heat pump is used for heating any one or any combination of more of power generation device condensate, boiler feed water, outlet flue gas of the ammonia desulphurization device and hot supply water.
7. A method for operating the ammonia desulfurization system of any one of claims 1-6, wherein waste heat recovery and condensate recovery are achieved and ammonia slip and fine particulate emissions are controlled, the method comprising:
operating an ammonia desulfurization plant wherein SO is to be contained2The flue gas is conveyed to an ammonia desulphurization device, and SO in the flue gas is removed by using absorption liquid containing ammonia desulfurizer2(ii) a And is
Operating the heat pump to extract heat from the circulating liquid in the circulating line as a heat source;
wherein, realize waste heat recovery through the heat pump, reduce the temperature with the solution of flue gas direct contact among the ammonia process desulphurization unit, reduce ammonia escape and tiny particle emission to realize the comdenstion water and retrieve.
8. The method according to claim 7, wherein the ammonia desulfurization system is according to any one of claims 4 to 6, wherein the first heat pump is operated to lower the temperature of the absorbent liquid to reduce the ammonia concentration and the aerosol generation in the absorption function section; and/or
The ammonia desulfurization system according to any one of claims 4 to 6, wherein the second heat pump provided to the fine particulate matter control function section is operated to lower the temperature of the washing liquid to condense water vapor in the flue gas in the fine particulate matter control function section and to reduce fine particulate matter entrained in the flue gas in the fine particulate matter control function section.
9. The method of claim 7 or 8, wherein the ammonia desulfurization system is operated such that: the temperature of the circulating liquid of the heat inlet pump as a heat source is controlled to be 20-70 ℃, and preferably 40-60 ℃; and/or controlling the temperature of the circulating liquid of the heat pump to be 10-60 ℃, preferably 20-50 ℃; and/or controlling the temperature of the flue gas of a functional area of the ammonia desulphurization device, which is connected with the heat pump, to be 20-70 ℃, preferably 40-60 ℃.
10. The method according to any one of claims 7 to 9, wherein the ammonia desulfurization system is according to claim 6, wherein the heat exchange device is operated such that the outlet flue gas temperature after heat exchange is controlled to be 30-60 ℃, preferably 35-50 ℃.
CN202210175019.4A 2022-02-25 2022-02-25 Ammonia desulphurization system and operation method thereof Pending CN114534478A (en)

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