CN209934418U - CO based on solid oxide fuel cell2Trapping system - Google Patents
CO based on solid oxide fuel cell2Trapping system Download PDFInfo
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- CN209934418U CN209934418U CN201920246473.8U CN201920246473U CN209934418U CN 209934418 U CN209934418 U CN 209934418U CN 201920246473 U CN201920246473 U CN 201920246473U CN 209934418 U CN209934418 U CN 209934418U
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Abstract
The utility model belongs to the field of CO recovery2The technical field, in particular to CO based on a solid oxide fuel cell2The capture system mainly comprises a heat exchanger and a membrane separation component, wherein the heat exchanger and the SOFC exhaust CO-containing gas2The tail gas outlet is communicated, and the membrane separation component comprises a membrane shell and CO2The separator and the tail gas inlet arranged on the membrane shell are communicated with the heat exchanger through a buffer device, and CO is introduced into the heat exchanger2The separator comprises a plurality of hollow hydrophobic ceramic membranes which are arranged in the membrane shell at intervals, and CO in the tail gas is separated under the action of external pressure2Can enter the inner cavity of the hollow hydrophobic ceramic membrane and is discharged from the end part of the hollow hydrophobic ceramic membrane, and water vapor in tail gas is recycled after condensation. The system has CO2High recovery efficiency, CO2High purity, simple process flow, easy operation, low energy consumption and the like.
Description
Technical Field
The utility model belongs to the field of CO recovery2The technical field, in particular to CO based on a solid oxide fuel cell2A capture system.
Background
The Solid Oxide Fuel Cell (SOFC) directly generates electricity through electrochemical reaction, breaks through the limitation of the traditional thermodynamic cycle carnot theorem, and has higher efficiency. Meanwhile, the SOFC has the advantages of diversified fuel types, high power generation efficiency, full solid structure, no liquid molten salt corrosion, relatively low cost, easy site selection, multiple fuel types, simple structure, capability of realizing thermoelectric power supply or mixing the SOFC and a steam turbine for secondary power generation and the like, and is one of ideal choices of future fossil fuel power generation technologies.
The unique internal structure of SOFC makes fossil fuel (such as methane) easy to generate electrochemical reaction with air, and the main component of tail gas generated by SOFC anode is CO2And water vapor, which is not mixed in the electrochemical reaction of fossil fuel and air, to discharge CO2The concentration is as high as 40%. CO 22Excessive discharge is causedOne of the main causes of ecological problems such as global warming and sea level rise. Therefore, how to recycle CO produced by SOFC2Has important research significance.
Chinese patent document CN107690722A discloses a catalyst containing CO2High efficiency fuel cell system with capture assembly and method thereof, wherein the high efficiency fuel cell system comprises a top cell assembly, a bottom fuel cell assembly and a separation assembly, and the method uses a condenser to cool a CO-containing fuel cell assembly2To obtain a dry anode exhaust comprising about 90% CO2And 9% water vapor, and CO2Separator for separating water from CO-containing gas2To separate CO again from the exhaust gas2To output with reduced CO2Separated gas content and separately outputting CO suitable for one or more of storage and external use2. However, the dried anode tail gas obtained by the method still contains a large amount of moisture, needs to be separated again, and has the disadvantages of complex operation process, high energy consumption for recovery and complex separation equipment.
SUMMERY OF THE UTILITY MODEL
Therefore, the to-be-solved technical problem of the utility model lies in overcoming among the prior art and retrieving separation CO in SOFC exhaust tail gas2The equipment is complex, the operation process is complicated, the recovery energy consumption is high, and the recovered CO is2The CO based solid oxide fuel cell has the problems of large amount of water and the like, thereby providing the CO based solid oxide fuel cell2A capture system.
Therefore, the utility model provides a following technical scheme:
the utility model provides a CO based on solid oxide fuel cell2The capture system comprises at least one group of heat exchangers, and the heat exchangers are connected with the CO-containing gas discharged by the solid oxide fuel cell2Communicating with the outlet of the tail gas of the water vapor to discharge CO-containing gas discharged by the solid oxide fuel cell2The tail gas of the water vapor is sent into the heat exchanger to exchange heat with a cooling medium;
the membrane separation assembly comprises a membrane shell and CO arranged in the membrane shell2A separator and a separator arranged in the separatorA tail gas inlet on the membrane shell, wherein the tail gas inlet is communicated with the heat exchanger through a buffer device, and the CO is discharged from the heat exchanger2The separator comprises a plurality of hollow hydrophobic ceramic membranes which are arranged in the membrane shell at intervals, and CO in the tail gas is separated under the action of external pressure2Can enter the inner cavity of the hollow hydrophobic ceramic membrane through the hollow hydrophobic ceramic membrane and is discharged from the end part of the hollow hydrophobic ceramic membrane, and CO is removed from tail gas2Other components are trapped between the inner wall of the membrane shell and the hollow hydrophobic ceramic membrane by the hollow hydrophobic ceramic membrane.
Further, the membrane separation module also comprises,
CO2the gas outlet is arranged at the top end of the membrane shell and is communicated with the inner cavity of the hollow hydrophobic ceramic membrane;
an exhaust valve arranged on the upper part of the membrane shell and used for exhausting tail gas to remove CO2Other components than water vapor;
the condensed water outlet is arranged at the bottom end of the membrane shell and is communicated with the inner cavity of the membrane shell so as to recycle the condensed water;
a temperature control device connected with the hollow hydrophobic ceramic membrane for controlling the CO2The temperature of the separator to condense water vapor trapped by the hollow hydrophobic ceramic membrane into condensed water.
Further, one end of the hollow hydrophobic ceramic membrane is closed to form a closed end, and the opposite end is open to form an open end, wherein CO entering the inner cavity of the hollow hydrophobic ceramic membrane2Outwardly from the open end;
the axial direction of the hollow hydrophobic ceramic membrane is consistent with the axial direction of the membrane shell.
Further, the tail gas inlet is arranged at the lower part of the membrane shell.
Further, the condensed water outlet is communicated with the cooling medium inlet of the heat exchanger, so that the condensed water and CO-containing discharged from the solid oxide fuel cell2The tail gas exchanges heat in the heat exchanger;
and the cooling medium outlet of the heat exchanger is communicated with the water vapor inlet of the solid oxide fuel cell.
Further, the heat exchanger consists of a first heat exchanger and a second heat exchanger which are sequentially communicated, and the first heat exchanger and the CO-containing solid oxide fuel cell of the solid oxide fuel cell2Is communicated with a tail gas outlet of the water vapor;
the condensed water outlet is respectively communicated with the first heat exchanger and the second heat exchanger, so that the condensed water is used as a cooling medium in the first heat exchanger and the second heat exchanger;
and the cooling medium outlet of the first heat exchanger is communicated with the water vapor inlet of the solid oxide fuel cell.
Further, the trapping system also comprises,
the water tank is arranged between the heat exchanger and the condensed water outlet;
CO2the recovery device comprises a plurality of sequentially communicated devices for compressing and collecting CO2And for collecting CO2The gas storage tank.
The utility model also provides a entrapment method of utilizing above-mentioned entrapment system, include the CO that contains that produces in the solid oxide fuel cell2Sending the tail gas of the water vapor and the tail gas of the water vapor into the heat exchanger for cooling; then the cooled CO is contained2The tail gas with the water vapor is sent into a membrane separation component for separation, and condensed water and CO are respectively collected2。
The raw material of the solid oxide fuel cell anode comprises water vapor, methane and/or petroleum; the cathode raw material comprises air or oxygen-enriched air;
the tail gas discharged by the anode comprises 40-60% of CO by volume fraction230-50% of water vapor and 0.5-10% of H2And CO.
CO-containing discharged from anode of solid oxide fuel cell2The temperature of the tail gas is 650-1000 ℃;
the cooled CO-containing2The temperature of the tail gas is 120-200 ℃;
the temperature of the membrane separation assembly is 20-60 ℃.
Further, the trapping method also comprises the step of taking the condensed water obtained after membrane separation as a cooling medium of the heat exchanger, wherein the condensed water forms the water vapor with the temperature of 100-150 ℃ after heat exchange in the heat exchanger, and the water vapor with the temperature of 100-150 ℃ is taken as the anode raw material of the solid oxide fuel cell to participate in the reaction.
The preparation method of the hollow hydrophobic ceramic membrane comprises the following steps:
preparing an inorganic membrane matrix: adding ceramic powder and acid into water, fully stirring to obtain a suspension, and then sequentially carrying out vacuum filtration, first drying, first roasting and polishing to obtain an inorganic membrane matrix;
preparing a hollow hydrophobic ceramic membrane: and coating the slurry containing the hydrophobic organic matters on the inorganic membrane substrate, and performing second drying and second roasting to obtain the hollow hydrophobic ceramic membrane.
The mass ratio of the ceramic powder to the acid to the water is (10-25): (1-5): (50-125);
the ceramic powder comprises at least one of alumina powder, silicon dioxide powder, carbon nano tube powder, titanium dioxide powder and molecular sieve powder, and the particle size of the ceramic powder is 0.1-10 mu m;
the mass fraction of the hydrophobic organic matters in the slurry containing the hydrophobic organic matters is 30-70%; the hydrophobic organic matter comprises at least one of polytetrafluoroethylene, polypropylene and polyvinylidene chloride;
the solvent of the slurry containing the hydrophobic organic matter comprises ethanol, isopropanol or methyl acetate; the slurry containing the hydrophobic organic matter also comprises 1-5 wt% of a binder, wherein the binder comprises polyvinyl alcohol, water glass or starch.
The first drying temperature is 80-120 ℃, and the first drying time is 2-10 h; the first roasting temperature is 800-1200 ℃, and the first roasting time is 4-12 h;
the second drying temperature is 80-120 ℃, and the second drying time is 6-12 h; the second roasting temperature is 200-300 ℃, and the second roasting time is 2-6 h.
The utility model discloses technical scheme has following advantage:
1. the utility model provides a CO based on solid oxide fuel cell2A capture system comprising at least one set of heat exchangers and membrane separation modules; CO-containing gas discharged by the heat exchanger and the solid oxide fuel cell2Communicating with the outlet of the tail gas of the water vapor to discharge CO-containing gas discharged by the solid oxide fuel cell2The tail gas of the water vapor is sent into the heat exchanger to exchange heat with a cooling medium; the membrane separation component comprises a membrane shell and CO arranged in the membrane shell2The separator and the tail gas inlet arranged on the membrane shell are communicated with the heat exchanger through a buffer device, and the CO is discharged from the heat exchanger2The separator comprises a plurality of hollow hydrophobic ceramic membranes which are arranged in the membrane shell at intervals, and CO in the tail gas is separated under the action of external pressure2Can enter the inner cavity of the hollow hydrophobic ceramic membrane through the hollow hydrophobic ceramic membrane and is discharged from the end part of the hollow hydrophobic ceramic membrane, and CO is removed from tail gas2Other components are trapped between the inner wall of the membrane shell and the hollow hydrophobic ceramic membrane by the hollow hydrophobic ceramic membrane, and the membrane separation module has CO2High separation efficiency, high water vapor recovery rate and the like. The utility model provides a entrapment system's entrapment is effectual, adopts the membrane separation subassembly that contains cavity hydrophobicity ceramic membrane can selectively filter nonpolar molecule CO2Thereby making CO2Compared with the method of direct condensation, solvent absorption and the like, the system can obtain CO by selective separation of other gas impurities such as water vapor and the like2The concentration is high, the water content is less, the secondary dehydration treatment is not needed, and the operation process is simple; and CO discharged from SOFC2The heat in the water vapor and the cooling medium in the heat exchanger can be transferred to the cooling medium in the heat exchanger, and then the cooling medium in the heat exchanger is recycled, so that the energy consumption for treating the waste gas is reduced, and the discharged water vapor is condensed and recycled, so that the recycling of the water vapor is realized, and the resources are saved; the system has the advantages of simple equipment, low energy consumption, easy operation, simple process flow, capability of realizing cyclic utilization of resources and the like.
2. The utility model also provides CO2The trapping method adopts the trapping system provided by the utility model, which comprises the step of collecting CO generated in the solid oxide fuel cell2Sending the tail gas of the water vapor and the tail gas of the water vapor into the heat exchanger for cooling; then the cooled CO is contained2The tail gas with the water vapor is sent into a membrane separation component for separation, and condensed water and CO are respectively collected2. The method includes treating CO emitted from the SOFC2Cooling with steam, and treating CO2Separating and cooling the CO and the water vapor, and recycling the water vapor after the water vapor is cooled and condensed to form liquid water to carry out CO separation2The method has simple operation, good trapping effect and recovered CO2High concentration of CO discharged by SOFC2And the steam is subjected to cooling circulation treatment, heat is transferred to the cooling medium of the heat exchanger, and the cooling medium in the heat exchanger is recycled, so that the energy consumption for treating waste gas is reduced, resources are saved, and CO is treated2And the water vapor is separated and cooled, so that the water vapor which is cooled and condensed to form liquid water is recycled, recycling is realized, and resources are saved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the technical solutions in the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a flow chart showing the structure of a trapping device for a solid oxide fuel cell according to example 1 of the present invention;
fig. 2 is a schematic structural view of a membrane separation module in a trapping device of a solid oxide fuel cell according to example 1 of the present invention;
reference numerals: 1-a condensate outlet; 2-tail gas inlet; 3-a membrane shell; 4-CO2A gas outlet; 5-tail encapsulation(ii) a 6-hollow hydrophobic ceramic membrane; 7-exhaust valve.
Detailed Description
The following examples are provided for better understanding of the present invention, and are not limited to the best mode, and do not limit the scope and content of the present invention, and any product that is the same or similar to the present invention, which is obtained by combining the features of the present invention with other prior art or the present invention, falls within the scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The present example provides a solid oxide fuel cell based CO2The trapping system, see fig. 1 and 2, specifically comprises,
at least one set of heat exchangers, the heat exchangers and CO discharged by the solid oxide fuel cell2Communicating with the outlet of the tail gas of the water vapor to discharge CO-containing gas discharged by the solid oxide fuel cell2The tail gas of the water vapor is sent into the heat exchanger to exchange heat with a cooling medium; the cooling medium outlet of the heat exchanger is communicated with the water vapor inlet of the solid oxide fuel cell;
the membrane separation assembly comprises a membrane shell 3 and CO arranged in the membrane shell2The separator and a tail gas inlet 2 arranged on the membrane shell, the tail gas inlet is communicated with the heat exchanger through a buffer device, and the CO is discharged from the heat exchanger2The separator comprises a plurality of hollow hydrophobic ceramic membranes 6 which are arranged in the membrane shell at intervals, and CO in the tail gas is separated under the action of external pressure2Can enter the inner cavity of the hollow hydrophobic ceramic membrane through the hollow hydrophobic ceramic membrane and is discharged from the end part of the hollow hydrophobic ceramic membrane, and CO is removed from tail gas2Other components are trapped on the inner wall of the membrane shell and the hollow hydrophobic ceramic membrane by the hollow hydrophobic ceramic membraneBetween the ceramic films; the membrane separation module further comprises CO2Gas outlet 4, exhaust valve 7, condensed water outlet 1 and temperature control device, CO2The gas outlet is arranged at the top end of the membrane shell and is communicated with the inner cavity of the hollow hydrophobic ceramic membrane; the exhaust valve is arranged at the upper part of the membrane shell and is used for exhausting tail gas to remove CO2Other components than water vapor; the condensed water outlet is arranged at the bottom end of the membrane shell and communicated with the inner cavity of the membrane shell to recycle the condensed water, and the condensed water outlet is communicated with the cooling medium inlet of the heat exchanger to ensure that the condensed water and CO-containing gas from the solid oxide fuel cell are mixed2Exchanging heat with the gas of the water vapor in the heat exchanger; the temperature control device is connected with the hollow hydrophobic ceramic membrane and is used for controlling the CO2The temperature of the separator is set to condense the water vapor trapped by the hollow hydrophobic ceramic membrane into condensed water, specifically, in this embodiment, the temperature control device is a refrigerator;
the water tank is arranged between the heat exchanger and the condensed water outlet;
CO2the recovery device comprises a plurality of sequentially communicated devices for compressing and collecting CO2And for collecting CO2The gas storage tank.
In this embodiment, the average pore diameter of the hollow hydrophobic ceramic membrane is 5 to 20 nm; one end of the hollow hydrophobic ceramic membrane is closed to form a closed end, the opposite end is opened to form an open end, and CO entering the inner cavity of the hollow hydrophobic ceramic membrane2Outwardly from the open end; specifically, the end part of the hollow hydrophobic ceramic membrane is encapsulated by a tail end enclosure 5; the axial direction of the hollow hydrophobic ceramic membrane is consistent with the axial direction of the membrane shell; the tail gas inlet is arranged at the lower part of the membrane shell;
the heat exchanger consists of a first heat exchanger and a second heat exchanger which are sequentially communicated, and the first heat exchanger and the CO of the solid oxide fuel cell2The cooling medium outlet of the first heat exchanger is communicated with the water vapor inlet of the solid oxide fuel cell,the second heat exchanger is communicated with a tail gas inlet of the membrane separation assembly through a buffer device, and specifically, the buffer device is a buffer tank; the condensed water outlet 1 is respectively communicated with the first heat exchanger and the second heat exchanger; in particular, the heat exchanger is a plate heat exchanger, and as a deformable embodiment, the heat exchanger is a tube heat exchanger.
Example 2
This example provides a CO2The trapping method of (1) is the trapping system described in example 1, and specifically comprises:
introducing air into the cathode of the SOFC fuel cell, introducing raw materials of methane and water vapor into the anode of the SOFC fuel cell to perform reforming oxidation reaction, and discharging CO with the temperature of 800 ℃ from the anode2And steam enter the heat exchanger 1 for heat exchange, and CO is generated after heat exchange2The temperature of the water vapor and the water vapor is 350 ℃, and the water in the water tank in the heat exchanger 1 is heated from 20 ℃ to 120 ℃ and enters the SOFC fuel cell anode as a raw material to be recycled; CO 22Continuously enters the heat exchanger 2 with the steam for heat exchange, and the CO after heat exchange2The temperature of the water vapor and the water vapor is 150 ℃, and the water in the water tank in the heat exchanger 2 is heated from 20 ℃ to 65 ℃ and used as external hot water for the device for recycling;
CO2and feeding the mixed vapor into a membrane separation assembly, controlling the temperature of the membrane separation assembly to be 50 ℃, condensing the mixed vapor into liquid water, feeding the condensed and separated water into a water tank to provide a water source, and feeding other components of CO2Then passes through the membrane layer and passes through a recovery device to the CO2Carrying out recovery storage;
the preparation method of the hollow hydrophobic ceramic membrane comprises the following specific steps:
inorganic film matrix: adding 50g of alumina powder (with the particle size of 0.3 mu m) and 5g of citric acid into 250g of deionized water, fully stirring to obtain a stable alumina suspension, then carrying out vacuum filtration to obtain an inorganic membrane matrix, drying at 100 ℃ for 6h, roasting at 1000 ℃ in a muffle furnace for 6h, and polishing by a sample polishing machine to obtain a flaky inorganic membrane matrix;
hollow hydrophobic ceramic membrane: polyvinylidene fluoride (PVDF) is dried in a vacuum drying oven at 60 ℃ for 8 hours, 30g of PVDF is dissolved in 70g of ethanol, 1 wt% of polyvinyl alcohol is added, the mixture is stirred at 60 ℃ for 12 hours, then the mixture is kept stand overnight to obtain slurry, the slurry is coated on the inorganic membrane substrate by a scraper of 150 microns, the inorganic membrane substrate is dried in an oven at 100 ℃ for 8 hours, and then the dried inorganic membrane substrate is roasted in a muffle furnace at 280 ℃ for 4 hours to obtain the hollow hydrophobic ceramic membrane.
CO2And (3) testing the trapping performance: simulating the anode tail gas of the solid oxide fuel cell, wherein the tail gas composition parameters are as follows: CO 2245% by volume of water vapour, 50% by volume of other gases (CO and H2) 5% by volume, at a discharge temperature of 800 ℃; introducing the simulated tail gas into a heat exchanger, and recovering CO2. The recovered CO was analyzed by GC gas chromatography2Content of 99.23%, recovered CO2The content of water vapor in the mixture was 0.34%.
Example 3
This example provides a CO2The trapping method of (1) is the trapping system described in example 1, and specifically comprises:
oxygen-enriched air is introduced into the cathode of the SOFC fuel cell, methane and water vapor enter the anode of the SOFC fuel cell to carry out reforming oxidation reaction, and CO with the temperature of 650 ℃ is discharged from the anode2And steam enter the heat exchanger 1 for heat exchange, and CO is generated after heat exchange2The temperature of the water and the steam is 200 ℃, the water in the water tank in the heat exchanger 1 is heated from 20 ℃ to 100 ℃ and enters the SOFC fuel cell anode as a raw material to be recycled; CO 22Continuously enters the heat exchanger 2 with the steam for heat exchange, and the CO after heat exchange2The temperature of the water vapor and the water vapor is 120 ℃, and the water in the water tank in the heat exchanger 2 is heated from 20 ℃ to 60 ℃ and used as external hot water for the device for recycling;
CO2and feeding the mixed vapor into a membrane separation assembly, controlling the temperature of the membrane separation assembly to be 30 ℃, condensing the mixed vapor into liquid water, feeding the condensed and separated water into a water tank to provide a water source, and feeding other components of CO2Then passes through the membrane layer and passes through a recovery device to the CO2Carrying out recovery storage;
the preparation method of the hollow hydrophobic ceramic membrane comprises the following specific steps:
inorganic film matrix: adding 50g of alumina powder (with the particle size of 0.3 mu m) and 5g of citric acid into 250g of deionized water, fully stirring to obtain a stable alumina suspension, then carrying out vacuum filtration to obtain an inorganic membrane matrix, drying at 100 ℃ for 6h, roasting at 1000 ℃ in a muffle furnace for 6h, and polishing by a sample polishing machine to obtain a flaky inorganic membrane matrix;
hollow hydrophobic ceramic membrane: polyvinylidene fluoride (PVDF) is dried in a vacuum drying oven at 60 ℃ for 8 hours, 50g of PVDF is dissolved in 50g of isopropanol, 5 wt% of starch is added, the mixture is stirred at 60 ℃ for 12 hours, then the mixture is kept still overnight to obtain slurry, the slurry is coated on an inorganic membrane substrate by a scraper of 150 microns, the inorganic membrane substrate is dried in an oven at 100 ℃ for 8 hours, and then the dried slurry is roasted in a muffle furnace at 280 ℃ for 4 hours to obtain the hollow hydrophobic ceramic membrane.
CO2And (3) testing the trapping performance: simulating the anode tail gas of the solid oxide fuel cell, wherein the tail gas composition parameters are as follows: CO 22Is 41% by volume, the volume fraction of water vapor is 52% by volume, and other gases (CO and H)2) The volume fraction is 7 percent, and the discharge temperature is 650 ℃; the simulated tail gas is introduced into a heat exchanger, and CO is recovered by adopting the trapping device and the trapping method of the embodiment2. The recovered CO was analyzed by GC gas chromatography2In an amount of 98.82%, recovered CO2The content of water vapor in the mixture was 0.48%.
Example 4
This example provides a CO2The trapping method of (1) is the trapping system described in example 1, and specifically comprises:
introducing air into the cathode of the SOFC fuel cell, introducing petroleum and steam into the anode of the SOFC fuel cell to perform reforming oxidation reaction, and discharging CO with the temperature of 1000 ℃ from the anode2And steam enter the heat exchanger 1 for heat exchange, and CO is generated after heat exchange2The temperature of the water and the steam is 400 ℃, the water in the water tank in the heat exchanger 1 is heated from 20 ℃ to 150 ℃ and enters the SOFC fuel cell anode as a raw material to be recycled; CO 22Continuously enters the heat exchanger 2 with the steam for heat exchange, and the CO after heat exchange2The temperature of the water vapor and the water vapor is 200 ℃, and the water in the water tank in the heat exchanger 2 is heated from 20 ℃ to 80 ℃ and used as external hot water for the device for recycling;
CO2and feeding the mixed vapor into a membrane separation assembly, controlling the temperature of the membrane separation assembly to be 30 ℃, condensing the mixed vapor into liquid water, feeding the condensed and separated water into a water tank to provide a water source, and feeding other components of CO2Then passes through the membrane layer and passes through a recovery device to the CO2Carrying out recovery storage;
the preparation method of the hollow hydrophobic ceramic membrane comprises the following specific steps:
inorganic film matrix: adding 25g of silicon dioxide powder (with the particle size of 5 mu m) and 5g of citric acid into 50g of deionized water, fully stirring to obtain a stable silicon dioxide suspension, then carrying out vacuum filtration to obtain an inorganic membrane matrix, drying at 80 ℃ for 10h, roasting at 1200 ℃ in a muffle furnace for 4h, and polishing by a sample polishing machine to obtain a flaky inorganic membrane matrix;
hollow hydrophobic ceramic membrane: polypropylene (PP) was dried in a vacuum oven at 50 ℃ for 12 hours, 70g of PP was dissolved in 30g of ethanol, 3 wt% of polyvinyl alcohol was added thereto, and the mixture was stirred at 60 ℃ for 12 hours, and then allowed to stand overnight to obtain a slurry, which was coated on the inorganic membrane substrate with a 150 μm doctor blade, dried in an oven at 80 ℃ for 12 hours, and then calcined in a 200 ℃ muffle furnace for 6 hours, to obtain the hollow hydrophobic ceramic membrane.
CO2And (3) testing the trapping performance: simulating the anode tail gas of the solid oxide fuel cell, wherein the tail gas composition parameters are as follows: CO 2248% by volume of water vapor, 49% by volume of other gases (CO and H)2) The volume fraction is 3 percent, and the discharge temperature is 1000 ℃; introducing the simulated tail gas into a heat exchanger, and recovering CO2. The recovered CO was analyzed by GC gas chromatography2Content of 98.76%, recovered CO2The content of water vapor in the mixture was 0.54%.
Example 5
This example provides a CO2The trapping method of (1) is the trapping system described in example 1, and specifically comprises:
introducing air into the cathode of the SOFC fuel cell, introducing methane and water vapor into the anode of the SOFC fuel cell to perform reforming oxidation reaction, and discharging CO with the temperature of 800 ℃ from the anode2And the steam enters the heat exchanger 1 for exchangingHeat, CO after heat exchange2The temperature of the water and the steam is 300 ℃, the water in the water tank in the heat exchanger 1 is heated from 20 ℃ to 140 ℃ and enters the SOFC fuel cell anode as a raw material to be recycled; CO 22Continuously enters the heat exchanger 2 with the steam for heat exchange, and the CO after heat exchange2The temperature of the water vapor and the water vapor is 150 ℃, and the water in the water tank in the heat exchanger 2 is heated from 20 ℃ to 70 ℃ and used as external hot water for the device for recycling;
CO2and feeding the mixed vapor into a membrane separation assembly, controlling the temperature of the membrane separation assembly to be 60 ℃, condensing the mixed vapor into liquid water, feeding the condensed and separated water into a water tank to provide a water source, and feeding other components of CO2Then passes through the membrane layer and passes through a recovery device to the CO2Carrying out recovery storage;
the preparation method of the hollow hydrophobic ceramic membrane comprises the following specific steps:
inorganic film matrix: 18g of TiO2Adding powder (particle size 10 μm) and 3g citric acid into 120g deionized water, and stirring to obtain stable TiO2Carrying out vacuum filtration on the suspension to obtain an inorganic membrane substrate, drying the inorganic membrane substrate at 120 ℃ for 2h, roasting the inorganic membrane substrate in a muffle furnace at 800 ℃ for 12h, and polishing the inorganic membrane substrate by a sample polishing machine to obtain a flaky inorganic membrane substrate;
hollow hydrophobic ceramic membrane: polytetrafluoroethylene (PTEF) is dried in a vacuum drying oven at 80 ℃ for 6 hours, then 60g of PTEF is dissolved in 40g of methyl acetate, 2 wt% of starch is added, the mixture is stirred at 60 ℃ for 12 hours, then the mixture is kept still overnight to obtain slurry, the slurry is coated on the inorganic membrane substrate by a scraper with the diameter of 150 mu m, and after the slurry is dried in an oven at 120 ℃ for 6 hours, the dried slurry is roasted in a muffle furnace at 300 ℃ for 2 hours to obtain the hollow hydrophobic ceramic membrane.
CO2And (3) testing the trapping performance: simulating the anode tail gas of the solid oxide fuel cell, wherein the tail gas composition parameters are as follows: CO 2245% by volume of water vapor, 50% by volume of other gases (CO and H)2) The volume fraction is 5 percent; introducing the simulated tail gas into a heat exchanger, and recovering CO2. The recovered CO was analyzed by GC gas chromatography2Content of 98.26%, recovered CO2The content of water vapor in the mixture was 0.84%.
Example 6
This example provides a CO2The trapping method of (1) is the trapping system described in example 1, and specifically comprises:
introducing air into the cathode of the SOFC fuel cell, introducing methane and water vapor into the anode of the SOFC fuel cell to perform reforming oxidation reaction, and discharging CO with the temperature of 900 ℃ from the anode2And steam enter the heat exchanger 1 for heat exchange, and CO is generated after heat exchange2The temperature of the water vapor and the water vapor is 350 ℃, the temperature of the water in the water tank in the heat exchanger 1 is raised from 20 ℃ to 130 ℃ and the water is used as a raw material to enter the SOFC fuel cell anode for recycling; CO 22Continuously enters the heat exchanger 2 with the steam for heat exchange, and the CO after heat exchange2The temperature of the steam and the water vapor is 180 ℃, and the water in the water tank in the heat exchanger 2 is heated from 20 ℃ to 65 ℃ and used as external hot water for the equipment for recycling; CO 22Continuously enters the heat exchanger 3 with the steam for heat exchange, and the CO after heat exchange2The temperature of the steam and the water vapor is 100 ℃, and the water in the water tank in the heat exchanger 3 is heated from 20 ℃ to 50 ℃ and used as external hot water for the equipment for recycling;
CO2and feeding the mixed vapor into a membrane separation assembly, controlling the temperature of the membrane separation assembly to be 20 ℃, condensing the mixed vapor into liquid water, feeding the condensed and separated water into a water tank to provide a water source, and feeding other components of CO2Then passes through the membrane layer and passes through a recovery device to the CO2Carrying out recovery storage;
the preparation method of the hollow hydrophobic ceramic membrane comprises the following specific steps:
inorganic film matrix: adding 12g of alumina powder (with the particle size of 1 mu m) and 2g of citric acid into 80g of deionized water, fully stirring to obtain a stable alumina suspension, then carrying out vacuum filtration to obtain an inorganic membrane matrix, drying at 110 ℃ for 8h, roasting at 900 ℃ in a muffle furnace for 10h, and polishing by a sample polishing machine to obtain a flaky inorganic membrane matrix;
hollow hydrophobic ceramic membrane: polytetrafluoroethylene (PTEF) is dried in a vacuum drying oven at 60 ℃ for 8 hours, then 30g of PTEF is dissolved in 70g of ethanol, 1 wt% of polyvinyl alcohol is added, the mixture is stirred at 60 ℃ for 12 hours, then the mixture is kept still overnight to obtain slurry, the slurry is coated on an inorganic membrane substrate by a scraper of 150 mu m, the inorganic membrane substrate is dried in an oven at 100 ℃ for 8 hours, and then the dried slurry is roasted in a muffle furnace at 280 ℃ for 4 hours to obtain the hollow hydrophobic ceramic membrane.
CO2And (3) testing the trapping performance: simulating the anode tail gas of the solid oxide fuel cell, wherein the tail gas composition parameters are as follows: CO 22Has a volume fraction of 47%, water vapor has a volume fraction of 49%, and other gases (CO and H)2) The volume fraction is 4 percent, and the discharge temperature is 800 ℃; introducing the simulated tail gas into a heat exchanger, and recovering CO2. The recovered CO was analyzed by GC gas chromatography2Content of 99.45%, recovered CO2The content of water vapor in the mixture was 0.28%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (5)
1. CO based on solid oxide fuel cell2An entrapment system, comprising,
at least one set of heat exchangers, the heat exchangers and the CO-containing discharged by the solid oxide fuel cell2Communicating with the outlet of the tail gas of the water vapor to discharge CO-containing gas discharged by the solid oxide fuel cell2The tail gas of the water vapor is sent into the heat exchanger to exchange heat with a cooling medium;
the membrane separation assembly comprises a membrane shell and CO arranged in the membrane shell2The separator and the tail gas inlet arranged on the membrane shell are communicated with the heat exchanger through a buffer device, and the CO is discharged from the heat exchanger2The separator comprises a plurality of hollow hydrophobic ceramic membranes which are arranged in the membrane shell at intervals, and CO in the tail gas is separated under the action of external pressure2Can enter the inner cavity of the hollow hydrophobic ceramic membrane through the hollow hydrophobic ceramic membrane and is discharged from the end part of the hollow hydrophobic ceramic membrane, and CO is removed from tail gas2Other components are trapped between the inner wall of the membrane shell and the hollow hydrophobic ceramic membrane by the hollow hydrophobic ceramic membrane.
2. The capture system of claim 1, wherein the membrane separation module further comprises,
CO2the gas outlet is arranged at the top end of the membrane shell and is communicated with the inner cavity of the hollow hydrophobic ceramic membrane;
an exhaust valve arranged on the upper part of the membrane shell and used for exhausting tail gas to remove CO2Other components than water vapor;
the condensed water outlet is arranged at the bottom end of the membrane shell and is communicated with the inner cavity of the membrane shell so as to recycle the condensed water;
a temperature control device connected with the hollow hydrophobic ceramic membrane for controlling the CO2The temperature of the separator to condense water vapor trapped by the hollow hydrophobic ceramic membrane into condensed water.
3. The capture system of claim 2, wherein the condensate outlet is in communication with a cooling medium inlet of the heat exchanger to allow condensate to be combined with CO-containing gas exhausted from the solid oxide fuel cell2The tail gas exchanges heat in the heat exchanger;
and the cooling medium outlet of the heat exchanger is communicated with the water vapor inlet of the solid oxide fuel cell.
4. The capture system of claim 2, wherein the heat exchanger comprises a first heat exchanger and a second heat exchanger arranged in series communication, the first heat exchanger being in communication with the CO-containing of the solid oxide fuel cell2Is communicated with a tail gas outlet of the water vapor;
the condensed water outlet is respectively communicated with the first heat exchanger and the second heat exchanger, so that the condensed water is used as a cooling medium in the first heat exchanger and the second heat exchanger;
and the cooling medium outlet of the first heat exchanger is communicated with the water vapor inlet of the solid oxide fuel cell.
5. The capture system of claim 1 or 2, further comprising,
the water tank is arranged between the heat exchanger and the condensed water outlet;
CO2the recovery device comprises a plurality of sequentially communicated devices for compressing and collecting CO2And for collecting CO2The gas storage tank.
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| CN201920246473.8U CN209934418U (en) | 2019-02-26 | 2019-02-26 | CO based on solid oxide fuel cell2Trapping system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821367A (en) * | 2019-02-26 | 2019-05-31 | 中国华电科工集团有限公司 | A kind of CO based on solid oxide fuel cell2Trapping system and method |
| CN111430753A (en) * | 2020-02-25 | 2020-07-17 | 国家能源投资集团有限责任公司 | Solid oxide fuel cell system, anode off-gas treatment system, and off-gas treatment method |
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2019
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821367A (en) * | 2019-02-26 | 2019-05-31 | 中国华电科工集团有限公司 | A kind of CO based on solid oxide fuel cell2Trapping system and method |
| CN109821367B (en) * | 2019-02-26 | 2023-11-28 | 中国华电科工集团有限公司 | CO based on solid oxide fuel cell 2 Trapping system and method |
| CN111430753A (en) * | 2020-02-25 | 2020-07-17 | 国家能源投资集团有限责任公司 | Solid oxide fuel cell system, anode off-gas treatment system, and off-gas treatment method |
| CN111430753B (en) * | 2020-02-25 | 2021-11-16 | 国家能源投资集团有限责任公司 | Solid oxide fuel cell system, anode off-gas treatment system, and off-gas treatment method |
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