CN113181751A - System and method for directly mineralizing flue gas carbon dioxide by using gypsum - Google Patents
System and method for directly mineralizing flue gas carbon dioxide by using gypsum Download PDFInfo
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Abstract
According to the system and the method for directly mineralizing flue gas carbon dioxide by using gypsum, the absorption tower can sequentially realize the processes of cooling, decarbonization and escaping ammonia capture on the desulfurized flue gas; wherein, lower part cooling zone bottom sets up the thick liquids district and cyclic connection upper portion ammonium bicarbonate sprays the layer, can realize the entrapment to the desulfurization flue gas waste heat, provide the heat for ammonium sulfate thick liquids cryoconcentration crystallization, middle part decarbonization section bottom sets up ammonium bicarbonate and holds the liquid layer and spray the layer formation circulation with ammonium bicarbonate, spray layer pipeline benefit ammonia through ammonium bicarbonate, can realize carrying out the decarbonization reaction that lasts to the cooling flue gas, realize lower part cooling zone and the regional separation of middle part decarbonization section simultaneously, the gypsum that upper portion deamination section set gradually along the direction of height sprays the layer, defroster and technology water spray the layer, the gypsum holds liquid layer and gypsum and sprays the layer formation circulation and spray, the realization lasts the entrapment process to the escape ammonia, this system structure is simple, and reasonable design, flue gas decarbonization and utilization cost are low, can realize the continuous online processing of big cigarette tolerance simultaneously.
Description
Technical Field
The invention belongs to the field of purification of atmospheric pollutants, and relates to a system and a method for directly mineralizing flue gas carbon dioxide by using gypsum.
Background
The problem of climate warming is a problem affecting the development of the whole human being, CO2Is the main reason of climate warming, and the large-scale coal-fired power generation equipment is CO2Maximum emission source, any desire to control CO on a large scale2Must be focused on CO in large combustion plants to cope with climate warming2And (4) trapping.
At present, the smoke decarbonization of a coal burner unit is mainly a carbon capture, utilization and storage (CCUS) technology which utilizes organic amine as an absorbent and CO in smoke2Reacting to generate water-soluble salt, heating the absorption liquid to realize CO2The technology has the problems of large energy consumption, low economic benefit, secondary pollution and the like, and the trapped carbon dioxide is mainly used for geological storage and oil displacement and has the problem of secondary leakage, so that the development of efficient and low-cost flue gas removal is urgently neededCarbon and resource utilization technology.
Currently, ammonia (NH) is used3) And gypsum (CaSO)4) With CO in the flue gas2Reacting to produce ammonium sulfate, i.e. fertilizer and calcium carbonate, CO2+2NH3+CaSO4·2H2O→(NH4)2SO4+CaCO3↓+2H2O, thereby realizing the decarbonization of the flue gas and mineralizing the flue gas.
Flue gas CO2The technology of directly mineralizing gypsum to co-produce ammonium sulfate and calcium carbonate is always a research hotspot. For example, chinese patent CN100551494C discloses a method and a system for removing carbon dioxide from flue gas of a power station by an ammonia process, wherein the final product of the method is ammonium bicarbonate fertilizer, and ammonium bisulfate slurry has a problem of mass decomposition during evaporation crystallization. Chinese patent document CN102303874B discloses a method for preparing ammonium sulfate by converting phosphogypsum by a polycrystalline method, wherein gypsum slurry of the method is from slurry of a phosphoric acid system, and a pretreatment and purification process is required to obtain a pure reactant. As described above, none of these patents relate to the development of a process technology for capturing and utilizing carbon coupled to a wet desulfurization system, and do not relate to the research of a process technology for internal circulation of an absorption tower.
Disclosure of Invention
Aiming at the problems of high cost and incapability of large-scale application in the process of mineralization and decarbonization in the prior art, the invention provides a system and a method for directly mineralizing flue gas carbon dioxide by using gypsum.
The invention is realized by the following technical scheme:
a system for directly mineralizing flue gas carbon dioxide by using gypsum is characterized by comprising an absorption tower, an ammonium sulfate crystal generating device and a calcium carbonate generating device;
the calcium carbonate generating device comprises a crystallizing tank and a gypsum slurry tank;
the absorption tower comprises a lower cooling section, a middle decarburization section and an upper deamination section which are sequentially arranged from bottom to top;
the bottom of the lower cooling section is provided with a slurry area, the top of the lower cooling section is provided with an ammonium sulfate spraying layer, the side wall of the lower cooling section is provided with a desulfurized flue gas inlet, the slurry area is positioned at the lower end of the desulfurized flue gas inlet, and the side wall of the slurry area is sequentially provided with a slurry backflow port, a slurry circulating outlet and a slurry outlet from high to low; the slurry circulating outlet is connected to the input end of the ammonium sulfate spraying layer through an ammonium sulfate circulating pump;
the input end of the ammonium sulfate crystal generating device is connected with the slurry output port, and the output end of the ammonium sulfate crystal generating device is connected with the slurry return port;
the bottom of the middle decarbonization section is provided with an ammonium carbonate liquid holding layer, the top of the middle decarbonization section is provided with an ammonium carbonate spraying layer, one side of the ammonium carbonate liquid holding layer is provided with an ammonium carbonate circulating outlet and an ammonium carbonate outlet, and the ammonium carbonate circulating outlet is connected to the input end of the ammonium carbonate spraying layer through an ammonium carbonate circulating pump; the ammonium carbonate outlet is connected with an ammonium carbonate inlet of the crystallizing tank; an ammonia water inlet is formed in the other side of the ammonium carbonate liquid holding layer;
the bottom of the upper deamination section is provided with a gypsum liquid holding layer, and the top of the upper deamination section is sequentially provided with a gypsum spraying layer, a demister and a process water spraying layer along the height direction; one side of the gypsum liquid-holding layer is provided with a gypsum circulating outlet, and the gypsum circulating outlet is connected to the gypsum spraying layer through a gypsum slurry tank.
Further, the ammonium sulfate crystal generating device comprises an ammonium sulfate discharge pump, an ammonium sulfate cyclone and a centrifuge;
the top outlet of the ammonium sulfate cyclone is connected with a slurry return port of the absorption tower, the side cut inlet is connected with a slurry output port of the absorption tower, and the bottom outlet is connected with a side cut inlet of the centrifuge;
the liquid phase outlet of the centrifuge is connected with the slurry reflux port of the absorption tower, and the solid phase outlet outputs ammonium sulfate crystals.
Further, the calcium carbonate generating device also comprises a calcium carbonate swirler;
the crystallization tank is provided with a gypsum inlet and a crystallization outlet, and the gypsum inlet is connected with a gypsum outlet of the gypsum slurry tank;
the outlet at the top of the calcium carbonate cyclone is sequentially connected with an evaporation ammonia remover and a vacuum belt conveyor, and the outlet at the bottom of the calcium carbonate cyclone is connected with a gypsum inlet of a crystallization tank;
the crystallization outlet of the crystallization tank is connected with the side cut inlet of the calcium carbonate cyclone.
Further, a stirrer is installed at the top of the crystallizing tank.
And further, a filtrate outlet of the vacuum belt conveyor is connected back to a slurry pool at the bottom of the absorption tower through a filtrate pump.
Further, a heat exchange coil is arranged in the evaporation ammonia remover.
Further, the heat exchange coil is connected with hot flue gas or hot steam.
Further, the top of the evaporation ammonia remover is provided with an ammonia gas outlet and is connected to the input end of the ammonium bicarbonate spraying layer.
A method for directly mineralizing flue gas carbon dioxide by using gypsum is characterized by comprising the following steps:
the desulfurized flue gas enters from the inlet of the absorption tower and is in countercurrent contact heat exchange with the circularly sprayed ammonium sulfate solution in the lower cooling section, so that the ammonium sulfate solution is evaporated and concentrated;
cooling the desulfurized flue gas to 20-30 ℃, allowing the desulfurized flue gas to enter a middle decarbonization section of the absorption tower, continuously supplying ammonia to the middle decarbonization section by an ammonia tank to form ammonia-containing absorption liquid for circulating spraying, and performing countercurrent contact reaction with low-temperature flue gas to remove CO2Decarbonizing the desulfurized flue gas to form decarbonized flue gas;
the decarbonized flue gas enters an upper deamination section and is in countercurrent contact with the gypsum solution which is sprayed circularly, escaping ammonia in the decarbonized flue gas is removed, and the flue gas is discharged cleanly through a demister and a process water spraying layer in sequence.
Further, in a crystallizing tank of the calcium carbonate generating device, the nitrogen-sulfur molar ratio of the ammonium bicarbonate solution to the desulfurized gypsum slurry is 2-2.5, and a large amount of calcium carbonate and gypsum are produced in the slurry at the bottom and are pumped into a calcium carbonate cyclone by a crystallizing discharge pump;
pumping the gypsum-rich bottom slurry in the calcium carbonate cyclone back to a crystallization tank through a gypsum reflux pump for continuous reaction, discharging the slurry at the top of the calcium carbonate cyclone to an evaporation ammonia remover, removing ammonia gas in a liquid phase, feeding the slurry into a vacuum belt conveyor to filter solid calcium carbonate, and pumping the ammonium sulfate filtrate back to a slurry pool at the bottom of an absorption tower through a filtrate pump;
and the slurry at the bottom of the absorption tower enters an ammonium sulfate cyclone and a centrifuge through an ammonium sulfate discharge pump to separate ammonium sulfate crystals, and the slurry in the ammonium sulfate cyclone flows back to the bottom of the absorption tower to continuously absorb heat, concentrate and crystallize.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a system for directly mineralizing flue gas carbon dioxide by using gypsum, which can sequentially realize the processes of cooling, decarbonization and escaping ammonia capture of desulfurized flue gas by arranging a lower cooling section, a middle decarbonization section and an upper deamination section in an absorption tower; wherein, lower part cooling zone bottom sets up the thick liquids district and cyclic connection upper portion ammonium bicarbonate sprays the layer, can realize the entrapment to the desulfurization flue gas waste heat, provide the heat for concentrated ammonium sulfate crystal, middle part decarbonization section bottom sets up ammonium bicarbonate and holds the liquid layer and spray the layer with ammonium bicarbonate and form the circulation, can realize carrying out the decarbonization reaction that lasts to the cooling flue gas, realize the regional separation of lower part cooling zone and middle part decarbonization section simultaneously, the gypsum that upper portion deamination section set gradually along the direction of height sprays the layer, defroster and technology water spray layer, the gypsum holds liquid layer and gypsum and sprays the layer and form the circulation and spray, the realization lasts the entrapment process to the escape ammonia, this system simple structure, and reasonable design, flue gas decarbonization and utilization cost are low, can realize the continuous on-line processing of big gas volume simultaneously.
Further, the calcium carbonate generating device is sequentially connected with the crystallizing tank, the calcium carbonate cyclone and the evaporation ammonia remover, wherein the crystallizing tank can collect and stir ammonium carbonate solution generated in the middle decarburization section and gypsum slurry generated in the upper deamination section and arrange the ammonium carbonate solution and the gypsum slurry into the calcium carbonate cyclone, the calcium carbonate cyclone rotates at a high speed, the gypsum slurry is guided to the crystallizing tank to continuously participate in reaction, the cost is saved, the utilization rate is improved, the calcium carbonate is guided to the evaporation ammonia remover, solid calcium carbonate and filtrate are obtained, and the filtrate is guided to the slurry pool of the lower cooling section to be recycled.
Further, ammonium sulfate crystal generation device connects cooling zone thick liquid pond, through ammonium sulfate swirler and centrifuge to the cooperation desulfurization flue gas waste heat can realize the low temperature evaporation crystal of ammonium sulfate, and the ammonium sulfate mainly acts on fertilizer, is applicable to various soil and crops, still can be used to the aspect such as weaving, leather, medicine simultaneously, and this system reasonable in design can reduction in production cost.
The invention relates to a method for directly mineralizing flue gas carbon dioxide by using gypsum, wherein desulfurized flue gas releases heat in a cooling section at the lower part of an absorption tower, an ammonium sulfate spraying layer continuously sprays the desulfurized flue gas at the same time, so that the desulfurized flue gas releases heat continuously, and an ammonium sulfate crystal generating device evaporates an ammonium sulfate solution by using the desulfurized flue gas to form ammonium sulfate crystals; the upper deamination section removes escaping ammonia in the decarburized flue gas by continuous gypsum solution spraying, so that the clean emission of the flue gas is realized; the method can realize large-scale application, and has the advantages of low production cost and high decarburization efficiency.
Further, in the calcium carbonate generation device, utilize the ammonium bicarbonate solution that the middle part decarbonization section decarbonization back generated and the gypsum thick liquid in the gypsum thick liquid jar to let in the crystallizer simultaneously, stirring reaction generates calcium carbonate and gypsum, separate gypsum and calcium carbonate solution through the calcium carbonate swirler, filter calcium carbonate filter cake and ammonium sulfate filtrating, ammonium sulfate filtrating gets into the absorption tower bottom once more, realize cyclic utilization, the problem of carbon dioxide's emission has been solved, the calcium carbonate filter cake that still separates out simultaneously can be used for wet flue gas desulfurization again, realize desulfurization system calcium circulation.
Drawings
FIG. 1 is a schematic diagram of a system for direct mineralization of flue gas carbon dioxide using gypsum in an embodiment of the present invention;
FIG. 2 is a schematic diagram of the absorption efficiency of a gypsum slurry tested under laboratory simulated flue gas conditions for ammonia slip in an embodiment of the present invention.
In the figure: the device comprises a process water spraying layer 1, a demister 2, a gypsum spraying layer 3, an absorption tower 4, an ammonium bicarbonate spraying layer 5, an ammonium sulfate spraying layer 6, a centrifuge 7, an ammonium sulfate swirler 8, an ammonium sulfate discharge pump 9, an ammonium sulfate circulating pump 10, an ammonium bicarbonate circulating pump 11, a crystallization tank 12, a crystallization discharge pump 13, a gypsum reflux pump 14, a filter pump 15, a stirrer 16, a gypsum circulating pump 17, a gypsum slurry tank 18, a gypsum slurry discharge pump 19, a calcium carbonate swirler 20, an evaporation ammonia remover 21, a vacuum belt conveyor 22, a heat exchange coil 23, a lower cooling section 24, a middle decarbonization section 25, an upper deamination section 26, an ammonium sulfate crystal generation device 27, an ammonia tank 28, an ammonia supply pump 29 and a calcium carbonate generation device 30.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a system for directly mineralizing flue gas carbon dioxide by using gypsum, which comprises an absorption tower 4, an ammonium sulfate crystal generating device 27 and a calcium carbonate generating device 30, as shown in figure 1; the absorption tower 4 comprises a lower cooling section 24, a middle decarburization section 25 and an upper deamination section 26 which are sequentially arranged along the height direction, wherein a slurry area is arranged at the bottom of the lower cooling section 24, an ammonium sulfate spraying layer 6 is arranged at the top of the lower cooling section, a desulfurized flue gas inlet is arranged on the side wall of the lower cooling section, the slurry area is positioned at the lower end of the desulfurized flue gas inlet, and a slurry backflow port, a slurry circulation outlet and a slurry outlet are sequentially arranged on the side wall of the slurry area from high to low; the input end of the ammonium sulfate crystal generating device 27 is connected with the slurry output port, and the output end is connected with the slurry return port, the slurry return port is highest in the height direction and is used for connecting and recovering the ammonium sulfate solution which is not crystallized in the ammonium sulfate crystal generating device 27; the slurry circulation outlet is provided with an ammonium sulfate circulating pump 10 and is connected with the input end of the ammonium sulfate spraying layer 6, so that the circulation spraying process of ammonium sulfate is realized.
The bottom of the middle decarbonization section 25 is provided with an ammonium carbonate liquid holding layer, the top of the middle decarbonization section is provided with an ammonium carbonate spraying layer 5, one side of the ammonium carbonate liquid holding layer is provided with an ammonium carbonate circulating outlet, the ammonium carbonate circulating outlet is provided with an ammonium carbonate circulating pump 11 and is connected with the input end of the ammonium carbonate spraying layer 5, and the ammonium carbonate circulating spraying process is realized; and one side of the side wall of the middle decarbonization section 25 is provided with an ammonium carbonate outlet and is connected with an ammonium carbonate input end of a calcium carbonate generation device 30; the absorption liquid is supplemented by ammonia through an ammonia supply pump 29 and an inlet pipeline connected with the ammonium bicarbonate spraying layer 5. The mass concentration of the ammonium carbonate solution in the ammonia-containing absorption liquid is 5% -20%, and the ammonium carbonate solution reacts with carbon dioxide in the desulfurized flue gas at the temperature of 20-30 ℃ to generate ammonium carbonate solution, and the reaction formula is as follows:
2NH3+CO2+H2O→(NH4)2CO3
(NH4)2CO3+CO2+H2O→NH4HCO3
NH4HCO3+NH3→(NH4)2CO3
the bottom of the upper deamination section 26 is provided with a gypsum liquid holding layer, and the top is sequentially provided with a gypsum spraying layer 3, a demister 2 and a process water spraying layer 1 along the height direction; a gypsum circulating outlet is formed in one side of the gypsum liquid-holding layer, specifically, the calcium carbonate generation device 30 comprises a crystallization tank 12 and a gypsum slurry tank 18, the gypsum circulating outlet is sequentially connected with the gypsum slurry tank 18 and a gypsum circulating pump 17 and flows back to the gypsum spraying layer 3 to form a gypsum circulating system, and meanwhile, escaping ammonia contained in the decarbonized flue gas can be trapped; wherein a gypsum liquid retaining layer separates the upper deamination section 26 and the middle decarbonization section 25 to form two separate zones.
Wherein, the ammonium bicarbonate holds the liquid layer and the gypsum holds the structure of liquid layer the same, all including holding cistern and liquid guide groove, holds the liquid groove interval and sets up and form the flue gas runner, the entering of the flue gas of being convenient for, and liquid guide groove back-off sets up in flue gas runner top, and the lateral wall stretches into adjacent liquid inslot that holds and sets up, and all hold mutual intercommunication between the liquid groove, the liquid that sprays of being convenient for to collect converge and circulate.
The ammonium sulfate crystal generating device 27 comprises an ammonium sulfate discharge pump 9, an ammonium sulfate cyclone 8 and a centrifuge 7; the liquid phase outlet of the ammonium sulfate cyclone 8 is connected with the slurry return port of the bottom cooling section 24, the solid phase outlet is connected with the side cut inlet of the centrifuge 7, and the side cut inlet is connected to the slurry output port of the absorption tower 4 through an ammonium sulfate discharge pump 9; the centrifuge 7 comprises a liquid phase outlet which mainly outputs ammonium sulfate solution at the top and a solid phase outlet which mainly outputs ammonium sulfate crystals, and the liquid phase outlet is connected with a slurry reflux port of the absorption tower 4; wherein, the top outlet of the ammonium sulfate swirler 8 and the ammonium sulfate solution outlet of the centrifuge 7 converge to the same pipeline to be connected with the slurry return port of the bottom cooling section; wherein the ammonium sulfate cyclone 8 and the centrifuge 7 are connected in series to realize a separation method matched with the centrifuge cyclone, thereby reducing the cost and improving the production efficiency.
The calcium carbonate generating device 30 comprises a crystallizing tank 12, a gypsum slurry tank 18 and a calcium carbonate cyclone 20; wherein, the top of the crystallizer 12 is provided with an ammonium bicarbonate inlet and a gypsum inlet, the bottom is provided with a crystallization outlet, the ammonium bicarbonate inlet is connected with an ammonium bicarbonate outlet of the middle decarbonization section 25, the gypsum inlet is connected with a gypsum outlet of the gypsum slurry tank 18, and the gypsum outlet of the gypsum slurry tank 18 is provided with a gypsum slurry discharge pump 19, wherein, the inside of the gypsum slurry tank 18 is provided with a stirrer 16, when in use, the stirrer 16 rotates to drive the gypsum slurry inside to fully react with the ammonium bicarbonate solution; the crystal discharge port is connected to a side cut inlet of the calcium carbonate cyclone 20 through a crystal discharge pump 13; the outlet at the top of the calcium carbonate cyclone 20 is sequentially connected with an evaporation ammonia remover 21 and a vacuum belt conveyor 22, and the outlet at the bottom is provided with a gypsum reflux pump 14 and is connected with the gypsum inlet of the crystallization tank 12.
Wherein, the bottom of the vacuum belt conveyor 22 is provided with a filtrate outlet, the filtrate outlet is provided with a filtrate pump 15 and is connected back to the slurry pool at the bottom of the absorption tower 4, the main component of the filtrate is ammonium sulfate solution, and the ammonium sulfate solution flows back to the slurry pool of the bottom cooling section 24 through the filtrate pump 15 for recycling; the inside of the evaporation ammonia remover 21 comprises a heat exchange coil 23, and the adopted heat source comprises hot flue gas or hot steam; the top of the evaporation ammonia remover 21 is provided with an ammonia gas outlet, and the ammonia gas outlet is connected to the input end of the ammonium bicarbonate spraying layer 5 of the middle decarbonization section 25, circularly added into the absorption liquid of the middle decarbonization section 25, participates in the reaction, improves the utilization rate and reduces the cost.
A method for directly mineralizing flue gas carbon dioxide by using gypsum comprises the following steps:
the desulfurization flue gas gets into by 4 desulfurization flue gas entrances of absorption tower, and the ammonium sulfate solution countercurrent contact heat transfer that sprays at lower part cooling section 24 and circulation realizes ammonium sulfate solution evaporative concentration, and wherein, when the thick liquid pond solid content of bottom cooling section 24 was greater than 10%, start ammonium sulfate discharge pump 9, carry out the evaporative concentration process of ammonium sulfate solution.
Cooling the desulfurized flue gas to 20-30 ℃, allowing the desulfurized flue gas to enter a middle decarbonization section 25 of the absorption tower 4, continuously supplying ammonia to the middle decarbonization section 25 by an ammonia tank 28 through an ammonia supply pump 29 to form ammonia-containing absorption liquid for circulating spraying, and performing countercurrent contact reaction with the low-temperature flue gas to remove CO2Form aDecarbonizing the flue gas;
the decarbonized flue gas enters the upper deamination section 26 and is in countercurrent contact with the gypsum solution which is circularly sprayed to remove escaping ammonia in the decarbonized flue gas, and the flue gas is sequentially subjected to demister 2 and process water spraying layer 1 to realize clean emission.
In a calcium carbonate generating device 30, an ammonium bicarbonate solution generated after decarbonization in a middle decarbonization section 25 and gypsum slurry in a gypsum slurry tank 18 are simultaneously introduced into a crystallizing tank 12, the nitrogen-sulfur molar ratio of the ammonium bicarbonate solution to the desulfurized gypsum slurry is 2-2.5, the slurry at the bottom of the crystallizing tank 12 contains a large amount of calcium carbonate and gypsum, and the calcium carbonate and gypsum are pumped into a side cut inlet of a calcium carbonate cyclone 20 through a crystallization discharge pump 13;
the bottom slurry rich in gypsum of the calcium carbonate cyclone 20 is pumped back to the crystallization tank 12 through a gypsum reflux pump 14 for continuous reaction, the slurry at the top of the calcium carbonate cyclone 20 is discharged to an evaporation ammonia remover 21, ammonia gas in a liquid phase is removed through the evaporation ammonia remover 21, the liquid phase enters a vacuum belt conveyor 22 for filtration, solid calcium carbonate is filtered out, and the filtered ammonium sulfate filtrate is pumped back to a slurry pool at the bottom of the absorption tower 4 through a filtrate pump 15;
the slurry at the bottom of the absorption tower 4 enters an ammonium sulfate cyclone 8 through an ammonium sulfate discharge pump 9, the slurry at the bottom of the cyclone contains a large amount of ammonium sulfate, the slurry enters a centrifuge 7 to separate ammonium sulfate crystals, and the slurry at the top of the ammonium sulfate cyclone 8 flows back to the bottom of the recovery tower 4 to be continuously concentrated and crystallized.
The invention provides a specific embodiment, which is used for testing the absorption effect of gypsum slurry on ammonia escape under the condition of laboratory simulated smoke:
the supply amount of the flue gas is set to be 5L/min, the ammonia escape amount is 50 muL/L, the absorption liquid 1 is gypsum slurry with the mass fraction of 20%, the absorption liquid 2 is pure water, the experiment is completed on a small spray tower test bed, the spray liquid-gas ratio is 2-20L/V, and the experiment result is shown in figure 2. Experimental results show that the deamination effect of gypsum slurry with the mass fraction of 20% is obviously better than that of pure water under the condition of the same liquid-gas ratio, and the ammonia escape rate can be controlled below 5 mu L/L when the liquid-gas ratio is more than 6.
The simulated smoke gas volume is set up to be 100m3A/h (Standard State) pilot system, CO in flue gas2The content of oxygen is 15%6 percent of the total nitrogen, the balance nitrogen, the temperature of the flue gas inlet of the absorption tower 4 is controlled between 50 ℃ and 60 ℃, and the temperature of the flue gas entering the middle decarbonization section 25 of the absorption tower 4 is controlled between 20 ℃ and 30 ℃;
the volume of a slurry pool of a cooling section 24 at the bottom of the absorption tower 4 is 500L, the height of a spraying layer between an upper section, a middle section and a lower section is 1.5m, each spraying layer is arranged in a single layer, a circulating pump adopts a mechanical diaphragm pump, and the circulating pressure of slurry is controlled to be 0.15MPa-0.4 MPa;
the inside of the evaporation ammonia remover 21 is provided with a snake-shaped heat exchange coil 23, steam flows in the coil to exchange heat, the temperature of slurry inside the evaporation ammonia remover 21 is controlled to be 50-70 ℃, and evaporated ammonia gas is introduced into an inlet pipeline of an ammonium bicarbonate circulating pump 11 through a pipeline to realize the recycling of ammonia;
the concentration of ammonia water absorption liquid of a decarbonization section 25 in the middle of the absorption tower 4 is controlled to be 1-5%, the initial mass concentration of gypsum slurry of a deamination section 26 on the upper part of the absorption tower 4 is 20%, and when ammonium sulfate slurry of a cooling section 24 at the bottom of the absorption tower 4 is concentrated to a solid content of more than 10% by an ammonium sulfate circulating pump 10, an ammonium sulfate discharge pump 9 is started;
the nitrogen-sulfur molar ratio of the ammonium bicarbonate solution entering the crystallization tank 12 to the desulfurized gypsum slurry is controlled to be 2-2.5, and a stirrer 16 is arranged at the top of the crystallization tank 12 and has the rotating speed of 130 r/min;
the final test result shows that the removal rate of carbon dioxide in the desulfurization flue gas can reach 78%, the ammonia escape at the outlet of the absorption tower 4 is less than 5 mu L/L, the purity of the obtained calcium carbonate is more than 98%, the purity of the ammonium sulfate is more than 99%, and the requirement of a fertilizer grade first-grade product is met.
Claims (10)
1. A system for directly mineralizing flue gas carbon dioxide by using gypsum is characterized by comprising an absorption tower (4), an ammonium sulfate crystal generating device (27) and a calcium carbonate generating device (30);
the calcium carbonate generation device (30) comprises a crystallization tank (12) and a gypsum slurry tank (18);
the absorption tower (4) comprises a lower cooling section (24), a middle decarburization section (25) and an upper deamination section (26) which are sequentially arranged from bottom to top;
a slurry area is arranged at the bottom of the lower cooling section (24), an ammonium sulfate spraying layer (6) is arranged at the top of the lower cooling section, a desulfurized flue gas inlet is formed in the side wall of the lower cooling section, the slurry area is positioned at the lower end of the desulfurized flue gas inlet, and a slurry backflow port, a slurry circulating outlet and a slurry outlet are sequentially formed in the side wall of the slurry area from high to low; the slurry circulating outlet is connected to the input end of the ammonium sulfate spraying layer (6) through an ammonium sulfate circulating pump (10);
the input end of the ammonium sulfate crystal generating device (27) is connected with a slurry output port, and the output end of the ammonium sulfate crystal generating device is connected with a slurry return port;
an ammonium carbonate liquid holding layer is arranged at the bottom of the middle decarbonization section (25), an ammonium carbonate spraying layer (5) is arranged at the top of the middle decarbonization section, an ammonium carbonate circulating outlet and an ammonium carbonate outlet are arranged on one side of the ammonium carbonate liquid holding layer, and the ammonium carbonate circulating outlet is connected to the input end of the ammonium carbonate spraying layer (5) through an ammonium carbonate circulating pump (11); the ammonium carbonate outlet is connected with an ammonium carbonate inlet of the crystallizing tank (12); an ammonia water inlet is formed in the other side of the ammonium carbonate liquid holding layer;
a gypsum liquid holding layer is arranged at the bottom of the upper deamination section (26), and a gypsum spraying layer (3), a demister (2) and a process water spraying layer (1) are sequentially arranged at the top along the height direction; one side of the gypsum liquid-holding layer is provided with a gypsum circulating outlet which is connected to the gypsum spraying layer (3) through a gypsum slurry tank (18).
2. The system for direct mineralization of flue gas carbon dioxide with gypsum according to claim 1, wherein the ammonium sulfate crystal generation means (27) comprises an ammonium sulfate discharge pump (9), an ammonium sulfate cyclone (8) and a centrifuge (7);
the top outlet of the ammonium sulfate cyclone (8) is connected with the slurry return port of the absorption tower (4), the side cut inlet is connected with the slurry output port of the absorption tower (4), and the bottom outlet is connected with the side cut inlet of the centrifuge (7);
a liquid phase outlet of the centrifuge (7) is connected with a slurry reflux port of the absorption tower (4), and a solid phase outlet outputs ammonium sulfate crystals.
3. The system for direct mineralization of flue gas carbon dioxide with gypsum according to claim 1, wherein the calcium carbonate generation unit (30) further comprises a calcium carbonate cyclone (20);
the crystallization tank (12) is provided with a gypsum inlet and a crystallization outlet, and the gypsum inlet is connected with a gypsum outlet of the gypsum slurry tank (18);
the outlet at the top of the calcium carbonate cyclone (20) is sequentially connected with an evaporation ammonia remover (21) and a vacuum belt conveyor (22), and the outlet at the bottom is connected with a gypsum inlet of the crystallization tank (12);
the crystallization outlet of the crystallization tank (12) is connected with the side cut inlet of the calcium carbonate cyclone (20).
4. A system for direct mineralization of flue gas carbon dioxide by gypsum according to claim 1 or 3, wherein the top of the crystallization tank (12) is equipped with a stirrer (16).
5. The system for directly mineralizing flue gas carbon dioxide by using gypsum according to claim 3, wherein a filtrate outlet of the vacuum belt conveyor (22) is connected back to a slurry pool at the bottom of the absorption tower (4) through a filtrate pump (15).
6. The system for directly mineralizing flue gas carbon dioxide by using gypsum according to claim 3, wherein a heat exchange coil (23) is arranged in the evaporation ammonia remover (21).
7. The system for directly mineralizing flue gas carbon dioxide by using gypsum according to claim 6, wherein the heat exchange coil (23) is connected with hot flue gas or hot steam.
8. The system for direct mineralization of flue gas carbon dioxide by gypsum according to claim 1, wherein the top of the evaporation ammonia remover (21) is provided with an ammonia gas outlet and is connected to the input end of the ammonium carbonate spraying layer (5).
9. A method for directly mineralizing flue gas carbon dioxide by using gypsum, which is characterized in that the system for directly mineralizing flue gas carbon dioxide by using gypsum based on any one of claims 1 to 8 comprises the following steps:
the desulfurized flue gas enters from the inlet of the absorption tower (4), and is in countercurrent contact heat exchange with the circularly sprayed ammonium sulfate solution in the lower cooling section (24), so that the ammonium sulfate solution is evaporated and concentrated;
cooling the desulfurized flue gas to 20-30 ℃, allowing the desulfurized flue gas to enter a middle decarbonization section (25) of the absorption tower (4), continuously supplying ammonia to the middle decarbonization section (25) by an ammonia tank (28), forming ammonia-containing absorption liquid for circular spraying, and carrying out counter-current contact reaction with the low-temperature flue gas to remove CO2Decarbonizing the desulfurized flue gas to form decarbonized flue gas;
the decarbonized flue gas enters an upper deamination section (26) and is in countercurrent contact with the gypsum solution sprayed circularly to remove escaping ammonia in the decarbonized flue gas, and the flue gas is discharged completely through a demister (2) and a process water spraying layer (1) in sequence.
10. The method for directly mineralizing flue gas carbon dioxide by using gypsum according to claim 9, wherein the nitrogen-sulfur molar ratio of the ammonium bicarbonate solution to the desulfurized gypsum slurry in the crystallizing tank (12) of the calcium carbonate generating device (30) is 2-2.5, and a large amount of calcium carbonate and gypsum are produced in the slurry at the bottom and are pumped into a calcium carbonate cyclone (20) through a crystallization discharge pump (13);
the bottom slurry rich in gypsum in the calcium carbonate cyclone (20) is pumped back into the crystallization tank (12) through a gypsum reflux pump (14) for continuous reaction, the slurry at the top of the calcium carbonate cyclone (20) is discharged to an evaporation ammonia remover (21), ammonia gas in a liquid phase is removed, solid calcium carbonate is filtered out through a vacuum belt conveyor (22), and ammonium sulfate filtrate in the calcium carbonate cyclone is pumped back into a slurry pool at the bottom of the absorption tower (4) through a filtrate pump (15);
the slurry at the bottom of the absorption tower (4) enters an ammonium sulfate cyclone (8) and a centrifuge (7) through an ammonium sulfate discharge pump (9) to separate ammonium sulfate crystals, and the slurry in the ammonium sulfate cyclone (8) flows back to the bottom of the absorption tower (4) to continuously absorb heat for concentration and crystallization.
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