CN117819550A - Carbon dioxide capture methods - Google Patents
Carbon dioxide capture methods Download PDFInfo
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- CN117819550A CN117819550A CN202211182959.2A CN202211182959A CN117819550A CN 117819550 A CN117819550 A CN 117819550A CN 202211182959 A CN202211182959 A CN 202211182959A CN 117819550 A CN117819550 A CN 117819550A
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- C01B32/00—Carbon; Compounds thereof
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
The invention provides a carbon dioxide capturing method. The carbon dioxide capturing method comprises the following steps: spraying the alkaline solution through the spraying structure so as to enable the alkaline solution flowing out of the spraying structure to chemically react with carbon dioxide gas in the gas to absorb the carbon dioxide gas; caching the solution subjected to the chemical reaction with the carbon dioxide gas through a caching structure, wherein the solution cached in the caching structure flows out through a spraying structure; detecting the concentration of hydroxyl and/or carbonate in the solution in the buffer structure in real time so as to supplement alkaline solution or water into the buffer structure according to the concentration of hydroxyl and carbonate; and if the hydroxyl concentration is detected to be less than or equal to m and the carbonate concentration is detected to be n, controlling the circulating pump to stop running so that the solution cached in the cache structure enters the electrolysis equipment for electrolysis. The invention effectively solves the problems of difficult control of the carbon dioxide gas capturing efficiency and the whole energy consumption of the carbon dioxide capturing system in the prior art.
Description
Technical Field
The invention relates to the technical field of carbon dioxide collection, in particular to a carbon dioxide capturing method.
Background
At present, the mainstream CO2 trapping methods at home and abroad mainly comprise a liquid amine adsorption method, a solid film adsorption method and the like. However, the above-described capturing method can capture only CO2 at a high concentration, and cannot capture CO2 in a wide concentration range, such as low concentration CO2 in air.
In the prior art, in order to solve the above problems, a method of using inorganic alkali such as potassium hydroxide as a liquid absorbent is adopted to capture carbon sources with wide concentration ranges such as air and flue gas, and the captured inorganic alkali lye is converted into carbonate aqueous solution and can be regenerated by an electrolysis method.
However, during electrolysis, too high or too low a carbonate concentration can lead to an increase in the cell voltage, increasing the system energy consumption. For the residual inorganic alkali, if the concentration of the residual alkali solution is too high, the hydroxyl in the inorganic alkali is completely consumed to electrolyze the carbonate, so that a large amount of electricity consumption is caused; if the concentration of the residual alkali liquor is too low, the trapping efficiency of the carbon dioxide gas in the trapping process cannot be effectively ensured. Therefore, the carbon dioxide gas capturing system in the prior art has a difficulty in controlling the capturing efficiency and the overall energy consumption of the carbon dioxide gas.
Disclosure of Invention
The invention mainly aims to provide a carbon dioxide trapping method, which aims to solve the problem that the trapping efficiency and the overall energy consumption of carbon dioxide in a carbon dioxide trapping system in the prior art are difficult to control.
In order to achieve the above object, the present invention provides a carbon dioxide capturing method comprising: spraying the alkaline solution through the spraying structure so as to enable the alkaline solution flowing out of the spraying structure to chemically react with carbon dioxide gas in the gas to absorb the carbon dioxide gas; caching the solution subjected to the chemical reaction with the carbon dioxide gas through a caching structure, wherein the solution cached in the caching structure flows out through a spraying structure; detecting the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure in real time, so as to supplement alkaline solution or water into the buffer structure according to the concentration of hydroxyl and the concentration of carbonate; in the process of detecting the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure in real time, if the concentration of hydroxyl is detected to be less than or equal to m and the concentration of carbonate is detected to be n, the circulating pump is controlled to stop running, so that the solution buffered in the buffer structure enters the electrolysis equipment for electrolysis.
Further, the method for flowing out the solution cached in the cache structure through the spraying structure comprises the following steps: the circulating pump is started to pump the solution buffered in the buffer structure into the spraying structure through the pipeline by the circulating pump.
Further, the method for supplementing the alkaline solution or water into the buffer structure according to the hydroxide concentration and/or the carbonate concentration comprises the following steps: if the hydroxyl concentration is detected to be smaller than m and the carbonate concentration is detected to be smaller than n, replenishing alkaline solution into the buffer structure; if the concentration of hydroxyl is detected to be less than or equal to m and the concentration of carbonate is detected to be greater than n, supplementing water into the buffer structure.
Further, the method for detecting the concentration of hydroxyl in the solution in the buffer structure in real time comprises the following steps: and (3) feeding the solution into a potentiometric titrator, dripping standard acid with calibrated H+ concentration into the solution, continuously stirring and recording a first-order differential curve of the volume of the standard acid and the potential of the solution in the titration process until the first-order differential curve of the potential of the solution reaches a first peak value, and calculating the concentration of hydroxyl of the solution by adopting the volume of the standard acid consumed at the moment.
Further, the method for detecting the carbonate concentration in the solution in the buffer structure in real time comprises the following steps: dropping standard acid with calibrated H+ concentration into the solution, continuously stirring and recording a first-order differential curve of the volume of the standard acid and the potential of the solution in the titration process until the first-order differential curve of the potential of the solution reaches a first peak value, recording the volume of the standard acid consumed at the moment as V1, continuously dropping the standard acid with calibrated H+ concentration into the solution, continuously stirring and recording the first-order differential curve of the volume of the standard acid and the potential of the solution in the titration process until the first-order differential curve of the potential of the solution reaches a second peak value, recording the volume of the standard acid consumed at the moment as V2, and calculating the carbonate concentration of the solution by adopting the difference value of V2 and V1.
Further, m is 0.1mol/L or more and 5mol/L or less; and/or n is 1mol/L or more and 6mol/L or less.
Further, m is 0.3mol/L or more and 2mol/L or less; and/or n is 2mol/L or more and 5.5mol/L or less.
Further, in the process that the solution cached in the cache structure enters the electrolysis equipment to carry out electrolysis, the carbon dioxide capturing method further comprises the following steps: the amount of electricity applied to the electrolysis apparatus is adjusted to control the ratio and/or the amount of carbon dioxide gas and hydrogen gas produced per unit time in the electrolysis apparatus.
Further, the method of adjusting the amount of electricity applied into the electrolysis apparatus includes: when the output ratio of the carbon dioxide gas to the hydrogen is 1, a preset electric quantity value Q applied to the electrolysis equipment is obtained, and nQ is increased on the basis of the preset electric quantity value Q so as to adjust the output ratio of the carbon dioxide gas to the hydrogen; where n=1, 2,3, …, N (n.ltoreq.n).
Further, in the process of adjusting the production ratio of the carbon dioxide gas and the hydrogen gas, the carbon dioxide capturing method further includes: detecting the content of electrolyte in the electrolysis equipment in real time, and adding the electrolyte into the electrolysis equipment if the content of the electrolyte is smaller than a preset value; wherein the electrolyte is alkali metal sulfate, or alkali metal nitrate or alkali metal phosphate.
Further, the method for caching the solution after the chemical reaction with the carbon dioxide gas through the caching structure comprises the following steps: setting at least two buffer structures for switching operation, wherein each buffer structure can selectively buffer the solution after the chemical reaction with the carbon dioxide gas is completed; and if the carbonate concentration in one buffer structure reaches a preset concentration value, deactivating the buffer structure, and activating the rest buffer structures.
By applying the technical scheme of the invention, the alkaline solution is sprayed through the spraying structure, so that the alkaline solution flowing out of the spraying structure and the carbon dioxide gas in the gas are subjected to chemical reaction, and the carbon dioxide gas is absorbed. In the process, the solution after the chemical reaction with the carbon dioxide gas is cached through the caching structure, and the solution cached in the caching structure flows out again through the spraying structure, so that the recycling of the solution is realized. In the process of capturing carbon dioxide gas, the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure are detected in real time, so that alkaline solution or water is supplemented into the buffer structure according to the concentration of hydroxyl and the concentration of carbonate, the concentration of hydroxyl and the concentration of carbonate in the solution in the final state are accurately controlled in an alkaline solution supplementing or water adding mode, the requirement of a subsequent electrolysis process is further met, the energy consumption of the whole system is reduced, the problem that the capturing efficiency and the whole energy consumption of the carbon dioxide gas of a carbon dioxide capturing system in the prior art are difficult to control is solved, and the capturing efficiency of the carbon dioxide capturing system is improved. And in the process of detecting the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure in real time, if the concentration of hydroxyl is detected to be less than or equal to m and the concentration of carbonate is detected to be n, controlling the circulating pump to stop running so that the solution buffered in the buffer structure enters the electrolysis equipment for electrolysis.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows a flow chart of an embodiment of a carbon dioxide capture method according to the present invention;
fig. 2 shows a treatment process for different concentrations of hydroxide and carbonate in solution within the buffer structure in the carbon dioxide capture process of fig. 1.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
It is noted that all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs unless otherwise indicated.
In the present invention, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used generally with respect to the orientation shown in the drawings or to the vertical, vertical or gravitational orientation; also, for ease of understanding and description, "left, right" is generally directed to the left, right as shown in the drawings; "inner and outer" refer to inner and outer relative to the outline of the components themselves, but the above-described orientation terms are not intended to limit the present invention.
In order to solve the problem that the carbon dioxide gas capturing efficiency and the whole energy consumption of a carbon dioxide capturing system in the prior art are difficult to control, the application provides a carbon dioxide capturing method.
Example 1
As shown in fig. 1 and 2, the carbon dioxide capturing method includes:
spraying the alkaline solution through the spraying structure so as to enable the alkaline solution flowing out of the spraying structure to chemically react with carbon dioxide gas in the gas to absorb the carbon dioxide gas;
caching the solution subjected to the chemical reaction with the carbon dioxide gas through a caching structure, wherein the solution cached in the caching structure flows out through a spraying structure;
detecting the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure in real time, so as to supplement alkaline solution or water into the buffer structure according to the concentration of hydroxyl and the concentration of carbonate;
in the process of detecting the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure in real time, if the concentration of hydroxyl is detected to be less than or equal to m and the concentration of carbonate is detected to be n, the circulating pump is controlled to stop running, so that the solution buffered in the buffer structure enters the electrolysis equipment for electrolysis.
By applying the technical scheme of the embodiment, the alkaline solution is sprayed through the spraying structure, so that the alkaline solution flowing out of the spraying structure and the carbon dioxide gas in the gas are subjected to chemical reaction, and the carbon dioxide gas is absorbed. In the process, the solution after the chemical reaction with the carbon dioxide gas is cached through the caching structure, and the solution cached in the caching structure flows out again through the spraying structure, so that the recycling of the solution is realized. In the process of capturing carbon dioxide gas, the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure are detected in real time, so that alkaline solution or water is supplemented into the buffer structure according to the concentration of hydroxyl and the concentration of carbonate, the concentration of hydroxyl and the concentration of carbonate in the solution in the final state are accurately controlled in an alkaline solution supplementing or water adding mode, the requirement of a subsequent electrolysis process is further met, the energy consumption of the whole system is reduced, the problem that the capturing efficiency and the whole energy consumption of the carbon dioxide gas of a carbon dioxide capturing system in the prior art are difficult to control is solved, and the capturing efficiency of the carbon dioxide capturing system is improved. And in the process of detecting the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure in real time, if the concentration of hydroxyl is detected to be less than or equal to m and the concentration of carbonate is detected to be n, controlling the circulating pump to stop running so that the solution buffered in the buffer structure enters the electrolysis equipment for electrolysis.
In this embodiment, the method for flowing out the solution buffered in the buffer structure through the spraying structure includes:
the circulating pump is started to pump the solution buffered in the buffer structure into the spraying structure through the pipeline by the circulating pump.
Specifically, in the process of capturing carbon dioxide gas by the carbon dioxide capturing system, the solution cached in the cache structure is pumped into the spraying structure through the pipeline by the circulating pump so as to reuse the solution, thereby realizing the recycling of the solution and avoiding the waste of resources. Meanwhile, the solution is pumped into the spraying structure through the circulating pump, so that the spraying structure can spray alkaline solution and CO2 to react, the spraying reliability of the spraying structure is further improved, and the operation reliability of the carbon dioxide capturing system is improved.
In this embodiment, the method for replenishing the alkaline solution or water into the buffer structure according to the hydroxide concentration and/or the carbonate concentration includes:
if the hydroxyl concentration is detected to be smaller than m and the carbonate concentration is detected to be smaller than n, replenishing alkaline solution into the buffer structure;
if the concentration of hydroxyl is detected to be less than or equal to m and the concentration of carbonate is detected to be greater than n, supplementing water into the buffer structure.
Specifically, an initial alkali liquor is placed in a buffer structure at the bottom of the carbon dioxide trapping system, a circulating pump is started to capture carbon dioxide gas, and the concentration of hydroxyl and carbonate in the buffer structure is detected in real time. When the hydroxyl concentration of the solution in the buffer structure is more than or equal to m and the carbonate concentration is less than n or the hydroxyl concentration is more than or equal to m and the carbonate concentration is more than or equal to n, the circulating pump continuously operates without adopting related measures; when the hydroxide concentration of the solution in the buffer structure is less than m and the carbonate concentration is less than n, starting an alkali liquor replenishing device and replenishing alkaline solution into the buffer structure, and continuously detecting the hydroxide and carbonate concentrations in the buffer structure; when the concentration of hydroxyl ions in the solution in the buffer structure is less than or equal to m and the concentration of carbonate ions is more than n, starting a water supplementing system and supplementing water into the buffer structure, and continuously detecting the concentration of hydroxyl ions and carbonate ions in the buffer structure.
Optionally, the method for detecting the hydroxide concentration in the solution in the buffer structure in real time includes:
and (3) feeding the solution into a potentiometric titrator, dripping standard acid with calibrated H+ concentration into the solution, continuously stirring and recording a first-order differential curve of the volume of the standard acid and the potential of the solution in the titration process until the first-order differential curve of the potential of the solution reaches a first peak value, and calculating the concentration of hydroxyl of the solution by adopting the volume of the standard acid consumed at the moment.
In this example, using a calibrated HCl solution, the actual concentration is 0.2404mol/L, and the actual concentration is slowly added into the solution as a titrant, titrating until the pH reaches below 2, recording the change of the standard acid addition volume and the pH of the solution, drawing the recorded standard acid addition volume and pH into a pH-V curve, calculating and drawing a Δph/Δv-V first-order value differential curve according to the recorded curve, taking the maximum value of the first-order value differential as an equivalent point, obtaining a titrated equivalent point volume through the first-order value differential, and calculating the corresponding equivalent point as EP1 shown in the change graph of the standard acid volume pH-V, wherein the equivalent point volume and the concentration are calculated to obtain the OH-concentration of the solution. The titration was about 10 minutes from the beginning to the end.
In other embodiments not shown in the drawings, the basicity of the solution is determined by neutral leaching, a calibrated concentration of HCl solution is used, a calibrated h+ concentration of 0.1107mol/L is slowly added dropwise to the solution as a titrant, the pH is about 3, the standard acid consumption volume and the change in pH of the solution are recorded, the recorded titration volume and pH are plotted as a pH-V plot, a first-order differential curve of Δph/Δv-V is calculated and plotted from the recorded plot, the standard acid volume corresponding to the maximum value of the first-order differential is taken as an equivalence point, the titration equivalence point volume is obtained by the first-order differential, the pH of the corresponding equivalence point is 5.02, and the OH-concentration of the solution is calculated. The titration was about 10 minutes from the beginning to the end.
In other embodiments not shown in the drawings, the basicity of the solution after one stage of acid adjustment is adopted, a calibrated HCl solution is used, the actual concentration is 0.1107mol/L and is slowly dripped into the solution as a titrant, the titration is carried out until the pH is about 3.8, the standard acid consumption volume and the pH change of the solution are recorded, the recorded titration volume and pH are drawn into a pH-V graph, a first-order differential curve of delta pH/delta V-V is calculated and drawn according to the recorded curve, the standard acid volume corresponding to the maximum value of the first-order differential is an equivalent point, the titration equivalent point volume is obtained through the first-order differential, the corresponding equivalent point pH is 4.42, and the OH-concentration of the solution is obtained through calculation. The titration was about 10 minutes from the beginning to the end.
In other embodiments not shown in the drawings, standard acid (i.e. a well known method for calibrating the H+ concentration of the aqueous solution of hydrochloric acid prepared) used in calibration experiments is used, and is carried out with reference to national standard GB/T601-2003. The method adopts twice calibration, firstly calibrates the concentration of standard alkali, and then uses the calibrated alkali standard solution with known concentration for calibrating standard acid. One example of the calibration of lye is: drying standard grade potassium hydrogen phthalate standard substance to constant weight at 105-110 ℃, dissolving 110g of sodium hydroxide in 100ml of carbon dioxide-free water, placing the solution in a closed polyethylene container until the solution is clear, taking 10.8ml of upper clear solution, and adding water to dilute the solution to 1000ml to prepare sodium hydroxide titration solution. 0.1377g of the potassium hydrogen phthalate standard substance dried to constant weight is weighed, added with water to 50-60 ml, stirred until the potassium hydrogen phthalate standard substance is completely dissolved, titrated by an automatic potentiometric titrator by using the endpoint judging principle of the embodiment and plotted, so as to obtain the volume of the equivalent point of titration by the first-order numerical differentiation of the graph, and the pH value of the equivalent point is 8.81, thereby calculating the concentration of sodium hydroxide titration solution. Titration was started to end for about 5 minutes. And (3) calibrating the hydrochloric acid titration solution by using the titration solution with the standard calibrated concentration. 27ml of hydrochloric acid was diluted with water to 1000ml to prepare a hydrochloric acid titration solution. 3.0000ml of the hydrochloric acid titration solution is added into a beaker, water is added to 50-60 ml, the mixture is stirred for 90 seconds, then the mixture is titrated by an automatic potentiometric titration instrument by using the endpoint judgment principle of the embodiment 1-3 and is drawn, and the volume of a titration equivalent point and the pH value of the equivalent point are obtained through the first-order numerical differentiation of the drawing. And calculating by using the concentration of the sodium hydroxide titration solution and the added volume of the hydrochloric acid to obtain the concentration of hydrochloric acid standard acid H+. Titration was started to end for about 5 minutes.
In this embodiment, the method for detecting the carbonate concentration in the solution in the buffer structure in real time includes:
dropping standard acid with calibrated H+ concentration into the solution, continuously stirring and recording a first-order differential curve of the volume of the standard acid and the potential of the solution in the titration process until the first-order differential curve of the potential of the solution reaches a first peak value, recording the volume of the standard acid consumed at the moment as V1, continuously dropping the standard acid with calibrated H+ concentration into the solution, continuously stirring and recording the first-order differential curve of the volume of the standard acid and the potential of the solution in the titration process until the first-order differential curve of the potential of the solution reaches a second peak value, recording the volume of the standard acid consumed at the moment as V2, and calculating the carbonate concentration of the solution by adopting the difference value of V2 and V1.
Optionally, m is 0.1mol/L or more and 5mol/L or less; and/or n is 1mol/L or more and 6mol/L or less. Therefore, the setting makes the values of m and n more flexible so as to meet different use requirements and working conditions.
Optionally, m is 0.3mol/L or more and 2mol/L or less; and/or n is 2mol/L or more and 5.5mol/L or less. Therefore, the setting makes the values of m and n more flexible so as to meet different use requirements and working conditions.
In this example, m is 0.1mol/L and n is 6mol/L. Spraying an alkaline solution through a spraying structure so as to enable the alkaline solution flowing out of the spraying structure to perform chemical reaction with carbon dioxide gas in the gas, detecting the concentration of hydroxyl and the concentration of carbonate in the solution in the buffer structure in real time in the process of supplementing the carbon dioxide gas, and continuously operating a circulating pump without adopting related measures when the concentration of hydroxyl and the concentration of carbonate in the solution in the buffer structure is more than or equal to 0.1 mol/and less than 6mol/L or the concentration of hydroxyl and more than 0.1 mol/and more than or equal to 6 mol/L; when the concentration of hydroxyl groups in the solution in the buffer structure is less than 0.1mol/L and the concentration of carbonate groups is less than 6mol/L, starting an alkali liquor supplementing device and supplementing alkaline solution into the buffer structure, and continuously detecting the concentration of hydroxyl groups and carbonate groups in the buffer structure; when the concentration of hydroxyl groups in the solution in the buffer structure is less than or equal to 0.1mol/L and the concentration of carbonate groups is more than 6mol/L, starting a water supplementing system and supplementing water into the buffer structure, and continuously detecting the concentration of hydroxyl groups and carbonate groups in the buffer structure. And if the hydroxyl concentration is detected to be less than or equal to 0.1mol/L and the carbonate concentration is detected to be 6mol/L, controlling the circulating pump to stop running so that the solution cached in the cache structure enters the electrolysis equipment for electrolysis.
It should be noted that the values of m and n are not limited thereto, and can be adjusted according to the working conditions and the use requirements.
The unit kWh/kg CO2 represents: during electrolysis, the electrolysis apparatus produces 1kg of electrical energy (kWh) consumed by co2 per electrolysis.
In this embodiment, in the process that the solution buffered in the buffer structure enters the electrolysis device to perform electrolysis, the carbon dioxide capturing method further includes:
the amount of electricity applied to the electrolysis apparatus is adjusted to control the ratio and/or the amount of carbon dioxide gas and hydrogen gas produced per unit time in the electrolysis apparatus.
Specifically, in the process of electrolyzing and regenerating alkali, absorbed carbon dioxide gas is released, high added value hydrogen is generated at the same time, and the carbon dioxide gas hydrogenation can synthesize various chemicals, so that a good solution foundation is provided for comprehensive utilization of the carbon dioxide gas, but different chemicals are different in the ratio of the carbon dioxide gas to the hydrogen, and how to control the output ratio of the carbon dioxide gas and the hydrogen at the same time in the process of regenerating inorganic alkali through electrolysis is also necessary. Electrolyte components are added into the electrolysis equipment to enhance conductivity, so that electrolysis energy consumption is reduced, and after the carbonate is electrolyzed, water can be electrolyzed to further generate hydrogen, so that the output ratio of carbon dioxide gas and hydrogen in unit time of the electrolysis equipment can be controlled by changing the applied electric quantity, and the application range of the system is greatly improved.
In this embodiment, the method of adjusting the amount of electricity applied to the electrolytic apparatus includes:
when the output ratio of the carbon dioxide gas to the hydrogen is 1, a preset electric quantity value Q applied to the electrolysis equipment is obtained, and nQ is increased on the basis of the preset electric quantity value Q so as to adjust the output ratio of the carbon dioxide gas to the hydrogen; where n=1, 2,3, …, N (n.ltoreq.n).
Specifically, taking a solution containing 1mol of carbonate groups treated in a unit time as an example, the electrolyte added to the electrolysis apparatus is potassium sulfate, and the concentration of potassium sulfate at the anode is set toAnd controlling the electric quantity applied by the electrolysis equipment to be 0.5mol/L, so that the electric quantity obtained by 1mol of carbonate solution is 53.6A.h, and the output ratio of carbon dioxide gas and hydrogen gas is 1:1. On the basis, when the applied electric quantity is increased by 53.6A.h, the output of carbon dioxide gas is 0, and more hydrogen is produced by 1mol, namely the output ratio of CO2 and H2 in unit time becomes 1:2, so that the output ratio of carbon dioxide gas and hydrogen gas is adjustable. The electric quantity applied by the electrolysis equipment is controlled in the embodiment, so that the electric quantity obtained by 1mol of carbonate-containing solution is 54.0 A.h, and the electric consumption of the electrolysis equipment is measured to be 3.30kWh/kg CO 2 The yield ratio of carbon dioxide gas and hydrogen gas was 1:1.01.
In this embodiment, in the process of adjusting the production ratio of the carbon dioxide gas and the hydrogen gas, the carbon dioxide capturing method further includes:
detecting the content of electrolyte in the electrolysis equipment in real time, and adding the electrolyte into the electrolysis equipment if the content of the electrolyte is smaller than a preset value; wherein the electrolyte is alkali metal sulfate, or alkali metal nitrate or alkali metal phosphate.
Optionally, the preset value is 0. Specifically, in the process of adjusting the output ratio of the carbon dioxide gas and the hydrogen, if the content of the electrolyte is smaller than a preset value, the electrolyte is added into the anode of the electrolysis equipment, the output ratio of the carbon dioxide gas and the hydrogen in unit time of the electrolysis equipment is controlled by changing the applied electric quantity, the overall energy consumption of the system is greatly reduced while the carbon dioxide trapping efficiency is ensured, and the carbon dioxide trapping system is convenient to control the trapping efficiency and the overall energy consumption of the carbon dioxide gas.
Alternatively, the alkali metal sulfate is potassium sulfate or sodium sulfate.
Alternatively, the alkali metal nitrate is potassium nitrate or sodium nitrate.
Alternatively, the alkali metal phosphate is potassium phosphate or sodium phosphate.
Alternatively, the alkaline solution is an alkali metal hydroxide.
Optionally, the method for caching the solution after the chemical reaction with the carbon dioxide gas through the caching structure comprises the following steps:
setting at least two buffer structures for switching operation, wherein each buffer structure can selectively buffer the solution after the chemical reaction with the carbon dioxide gas is completed; and if the carbonate concentration in one buffer structure reaches a preset concentration value, deactivating the buffer structure, and activating the rest buffer structures.
In this embodiment, two buffer structures are provided, when the carbonate concentration in the first buffer structure reaches a preset concentration value, the second buffer structure is started to capture CO2 through the alkali liquor in the buffer structure, the carbonate solution in the first buffer structure is emptied, then fresh alkali liquor is replenished, and after the carbonate concentration in the second buffer structure reaches the preset concentration value, the first buffer structure is started again, so that the process is alternately repeated.
Alternatively, the alkali metal hydroxide is potassium oxide or sodium hydroxide.
In the present embodiment, the carbon dioxide capturing method is applied to a gas absorbing system for absorbing carbon dioxide gas. The gas absorption system comprises a shell and a gas absorption assembly, wherein the gas absorption assembly is provided with a gas inlet and a gas outlet, and the gas inlet is opposite to the gas outlet. The gas absorption assembly is arranged in the shell and positioned at the downstream of the gas pretreatment device, and comprises a liquid supply device and a spraying structure which are communicated with each other and used for providing alkaline solution; the alkaline solution flowing out of the spray structure chemically reacts with the carbon dioxide gas in the gas to absorb the carbon dioxide gas.
Alternatively, the gas absorption system is a cross-flow absorption system or a countercurrent absorption system. The cross flow type absorption system is characterized in that the air inlet direction and the exhaust direction of air or smoke are consistent. The countercurrent absorption system is arranged in an included angle between the air inlet direction and the exhaust direction of air or flue gas.
Optionally, the spray structure is a spray head.
Optionally, the gas absorbing assembly comprises a packing and a water trap. The filler is positioned below the spraying structure. The water collector is arranged opposite to the filler. Therefore, a sufficient contact surface is provided for the CO2 and the alkaline solution through the filler, so that the CO2 in the air or the flue gas fully reacts with the alkaline solution, and the trapping and absorbing efficiency of the gas absorption assembly on the CO2 is further improved. The water collector is used for recycling the absorption liquid in the gas absorption assembly so as to reduce the drift of fine water drops clamped in the gas discharged from the gas absorption assembly. Meanwhile, the setting position of the water receiver is more flexible by the aid of the setting, so that different use requirements and working conditions are met, and processing flexibility of workers is improved.
Specifically, the alkaline solution falls into the filler from the spray structure in the form of droplets, flows in the filler in the form of a liquid film, passes through the filler, and then falls into the buffer structure in the form of droplets. The pretreated gas is fully contacted with alkaline solution in a water spraying area and a filler of the gas absorption assembly, so that CO2 in air or flue gas is subjected to chemical reaction with the alkaline solution, CO2 is captured, the captured CO2 exists in a buffer structure in the form of carbonate and bicarbonate ions, and the reacted solution is conveyed to a subsequent process system for treatment through a circulating pump. Meanwhile, the buffer structure is matched with a first liquid supply device to supplement water and hydroxyl consumed in the solution.
Optionally, the filler is a film type water spray filler.
Optionally, the water collector is a PVC water collector, and the water collector is supported by a bracket.
In this embodiment, the gas absorbing assembly further includes a buffer structure. The buffer structure is positioned below the filler and is used for buffering the solution after the chemical reaction with the carbon dioxide gas is completed. Therefore, the solution after the chemical reaction with the carbon dioxide gas is stored through the buffer structure, and on one hand, the solution is convenient to carry out post-treatment; on the other hand, the recycling of the solution can be realized, so that the resource waste is avoided.
In this embodiment, the buffer structure and the liquid supply device are the same structure, at the initial stage of operation of the gas absorption system, an alkaline solution is placed in the buffer structure, and is sprayed to the filler through the spraying structure to react with CO2 in air or flue gas, and the solution after the reaction is buffered in the buffer structure so as to enter the spraying structure again to continue spraying, so that the alkaline solution can be recycled, until carbonate in the alkaline solution reaches a preset concentration value, at this time, capturing and absorbing of CO2 are stopped, and the solution in the buffer structure is replaced by the alkaline solution.
It should be noted that the relationship between the buffer structure and the liquid supply device is not limited thereto, and may be adjusted according to the working condition and the use requirement. Optionally, the buffer structure is communicated with the liquid supply device, so that alkaline solution is provided into the spraying structure through the liquid supply device, and the solution after the reaction with CO2 is buffered in the buffer structure, so that the solution enters the spraying structure again to continue spraying.
Optionally, the cache structure is one; alternatively, the number of cache structures may be plural, and the plural cache structures may be selectively put into use. Therefore, in the operation process of the gas absorption system, the use state (in use or not) of the buffer structure can be adjusted according to the concentration of carbonate in the buffer structure so as to supplement fresh alkaline solution into the spray structure, and the gas absorption system can rapidly and efficiently capture CO2.
Optionally, the buffer structure is a plurality of, and the gas absorption assembly further comprises a main pipeline, a plurality of branch pipelines and a plurality of control valves. The first end of the main pipeline is communicated with the spraying structure. The branch pipelines are arranged in one-to-one correspondence with the cache structures, and two ends of each branch pipeline are respectively communicated with the corresponding cache structure and the second end of the main pipeline. The control valves are arranged in one-to-one correspondence with the branch pipelines, and each control valve controls the on-off state of the corresponding branch pipeline. Wherein at any time at least one control valve is in an open state. Therefore, the on-off state of the branch pipeline corresponding to the control valve is controlled through the control valve so as to control the use state of the buffer structure communicated with the branch pipeline, so that the control of the use state of the buffer structure by a worker is easier and simpler, and the control difficulty is reduced. Meanwhile, the plurality of buffer structures are arranged in parallel, and at any moment, at least one buffer structure is controlled to be put into use so as to provide alkaline solution for the spraying structure.
In this embodiment, the gas absorbing assembly further comprises a circulation pump. The circulating pump is arranged on the main pipeline or the branch pipeline and is used for pumping the solution entering the buffer structure into the spraying structure. Like this, in with solution pump to spray the structure through the circulating pump to ensure to spray the structure and can spray out alkaline solution and CO2 and react, and then promoted the spraying reliability that sprays the structure, promoted the operational reliability of gas absorption system.
Example two
The carbon dioxide capturing method in the second embodiment is different from that in the first embodiment in that: the values of m and n are different, and the electric quantity applied by the electrolysis equipment is controlled.
In this example, m is 0.3mol/L, n is 5.5mol/L, and the electric quantity applied by the electrolysis apparatus is controlled so that the electric quantity obtained by the solution containing 1mol of carbonate is 55.1 A.h, and the electric consumption of the electrolysis apparatus is 3.36kWh/kgCO 2 The yield ratio of carbon dioxide gas and hydrogen gas was 1:1.03.
Example III
The carbon dioxide capturing method in the third embodiment is different from that in the first embodiment in that: the values of m and n are different, and the electric quantity applied by the electrolysis equipment is controlled.
In this example, m is 5mol/L and n is 1mol/L, and the power consumption of the electrolysis apparatus is 11.46kWh/kgCO 2 The electric quantity applied by the electrolysis equipment is controlled, so that the electric quantity obtained by 1mol of carbonate-containing solution is 187.6A.h, and the output ratio of carbon dioxide gas and hydrogen gas is 1:3.5.
Example IV
The carbon dioxide capturing method in the fourth embodiment is different from that in the first embodiment in that: the values of m and n are different, and the electric quantity applied by the electrolysis equipment is controlled.
In this example, m is 0.1mol/L, n is 5.3mol/L, and the electric quantity applied by the electrolysis apparatus is controlled so that the electric quantity obtained by the solution containing 1mol of carbonate is 54.1 A.h, and the electric consumption of the electrolysis apparatus is 3.29kWh/kgCO 2 The yield ratio of carbon dioxide gas and hydrogen gas is 1:1.
Example five
The carbon dioxide capturing method in the fifth embodiment differs from the first embodiment in that: the values of m and n are different, and the electric quantity applied by the electrolysis equipment is controlled.
In this example, m is 2.5mol/L, n is 0.5mol/L, and the electric power applied by the electrolysis apparatus is controlled so that the electric power obtained from the solution containing 1mol of carbonate is 187.6A.h, and the electric power consumption of the electrolysis apparatus is 11.83kWh/kgCO 2 The yield ratio of carbon dioxide gas and hydrogen gas was 1:3.5.
Example six
The carbon dioxide capturing method in the sixth embodiment is different from that in the first embodiment in that: the electric quantity applied by the electrolysis equipment is controlled to be different.
In this example, the electric power applied by the electrolysis apparatus was controlled so that the electric power obtained by 1mol of the carbonate-containing solution was 107.2 A.h, and the electric power consumption of the electrolysis apparatus was measured to be 6.63kWh/kgCO 2 The yield ratio of carbon dioxide gas and hydrogen gas was 1:2.01.
The results of the power consumption of the electrolysis apparatus and the ratio of carbon dioxide gas to hydrogen gas produced, which were measured in the above-described all examples, are shown in Table 1.
Table 1 Table shows results of the ratio of the output of carbon dioxide gas to the output of hydrogen gas in each example of the power consumption of the electrolysis apparatus
| Electricity consumption of electrolysis plant (kWh/kgCO) 2 ) | Production ratio of carbon dioxide gas and Hydrogen gas (vol%) | |
| Example 1 | 3.30 | 1:1.01 |
| Example 2 | 3.36 | 1:1.03 |
| Example 3 | 11.46 | 1:3.5 |
| Example 4 | 3.29 | 1:1 |
| Example 5 | 11.83 | 1:3.5 |
| Example 6 | 6.63 | 1:2.01 |
From the above comparison, the following can be concluded:
1. as can be seen from comparing embodiments 3 and 5, by the carbon dioxide capturing method described in the present application, the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure can be precisely controlled, and when the solution in the buffer structure is sent to the electrolysis device for electrolysis, the concentration ranges of hydroxyl and carbonate in the solution, including but not limited to the preferred range of the present application, are limited within the preferred range of the present application, which is favorable for reducing the energy consumption of the electrolysis device, thereby reducing the process cost of the carbon dioxide capturing system, and effectively solving the problems of difficult control of the capturing efficiency and the overall energy consumption of the carbon dioxide gas of the carbon dioxide capturing system in the prior art.
2. As can be seen from comparing examples 1 to 6, the carbon dioxide capturing method described in the present application realizes that the output ratio of carbon dioxide gas and hydrogen gas in the electrolysis process is adjustable, and can flexibly adjust the output ratio of carbon dioxide gas and hydrogen gas in the system according to the actual requirement of the downstream carbon dioxide gas utilization device, thereby greatly improving the application range of the system.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
the alkaline solution is sprayed through the spraying structure, so that the alkaline solution flowing out of the spraying structure and carbon dioxide gas in the gas are subjected to chemical reaction, and the carbon dioxide gas is absorbed. In the process, the solution after the chemical reaction with the carbon dioxide gas is cached through the caching structure, and the solution cached in the caching structure flows out again through the spraying structure, so that the recycling of the solution is realized. In the process of capturing carbon dioxide gas, the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure are detected in real time, so that alkaline solution or water is supplemented into the buffer structure according to the concentration of hydroxyl and the concentration of carbonate, the concentration of hydroxyl and the concentration of carbonate in the solution in the final state are accurately controlled in an alkaline solution supplementing or water adding mode, the requirement of a subsequent electrolysis process is further met, the energy consumption of the whole system is reduced, the problem that the capturing efficiency and the whole energy consumption of the carbon dioxide gas of a carbon dioxide capturing system in the prior art are difficult to control is solved, and the capturing efficiency of the carbon dioxide capturing system is improved. And in the process of detecting the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure in real time, if the concentration of hydroxyl is detected to be less than or equal to m and the concentration of carbonate is detected to be n, controlling the circulating pump to stop running so that the solution buffered in the buffer structure enters the electrolysis equipment for electrolysis.
It will be apparent that the embodiments described above are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
It should be noted that the terms "first," "second," and the like in the description and claims of the present application and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that embodiments of the present application described herein may be implemented in sequences other than those illustrated or described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A carbon dioxide capture method, comprising:
spraying an alkaline solution through a spraying structure to enable the alkaline solution flowing out of the spraying structure to chemically react with carbon dioxide gas in gas so as to absorb the carbon dioxide gas;
caching the solution subjected to the chemical reaction with the carbon dioxide gas through a caching structure, wherein the solution cached in the caching structure flows out through the spraying structure;
detecting the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure in real time, so as to supplement alkaline solution or water into the buffer structure according to the concentration of hydroxyl and the concentration of carbonate;
in the process of detecting the concentration of hydroxyl and/or the concentration of carbonate in the solution in the buffer structure in real time, if the concentration of hydroxyl is detected to be less than or equal to m and the concentration of carbonate is detected to be n, the circulating pump is controlled to stop running, so that the solution buffered in the buffer structure enters the electrolysis equipment for electrolysis.
2. The method of claim 1, wherein the method of flowing the solution buffered in the buffer structure out through the spray structure comprises:
and starting the circulating pump to pump the solution buffered in the buffer structure into the spraying structure through the pipeline by the circulating pump.
3. The method of claim 1, wherein the replenishing of the alkaline solution or water into the buffer structure according to the hydroxide concentration and/or the carbonate concentration comprises:
if the hydroxyl concentration is detected to be smaller than m and the carbonate concentration is detected to be smaller than n, replenishing alkaline solution into the buffer structure;
and if the hydroxyl concentration is detected to be less than or equal to m and the carbonate concentration is detected to be greater than n, supplementing water into the buffer structure.
4. The method of claim 1, wherein the method of detecting the concentration of hydroxyl groups in the solution in the buffer structure in real time comprises:
and (3) feeding the solution into a potentiometric titrator, dripping standard acid with calibrated H+ concentration into the solution, continuously stirring and recording a first-order differential curve of the volume of the standard acid and the potential of the solution in the titration process until the first-order differential curve of the potential of the solution reaches a first peak value, and calculating the hydroxyl concentration of the solution by adopting the volume of the standard acid consumed at the moment.
5. The method of claim 1, wherein the method of detecting the carbonate concentration in the solution in the buffer structure in real time comprises:
and (3) feeding the solution into a potentiometric titrator, dripping standard acid with calibrated H+ concentration into the solution, continuously stirring and recording a first differential curve of the volume of the standard acid and the potential of the solution in the titration process until the first differential curve of the potential of the solution reaches a first peak value, recording the volume of the standard acid consumed at the moment as V1, continuously dripping the standard acid with calibrated H+ concentration into the solution, continuously stirring and recording the first differential curve of the volume of the standard acid and the potential of the solution in the titration process until the first differential curve of the potential of the solution reaches a second peak value, recording the volume of the standard acid consumed at the moment as V2, and calculating the carbonate concentration of the solution by adopting the difference value between V2 and V1.
6. The carbon dioxide capturing method according to claim 1, wherein m is 0.1mol/L or more and 5mol/L or less; and/or n is 1mol/L or more and 6mol/L or less.
7. The carbon dioxide capturing method according to claim 6, wherein m is 0.3mol/L or more and 2mol/L or less; and/or n is 2mol/L or more and 5.5mol/L or less.
8. The method of claim 1, wherein the solution buffered in the buffer structure enters the electrolysis device for electrolysis, and the method further comprises:
and adjusting the electric quantity applied to the electrolysis equipment to control the output ratio and/or the output of the carbon dioxide gas and the hydrogen gas in the electrolysis equipment in unit time.
9. The carbon dioxide capture method of claim 8, wherein the method of adjusting the amount of electricity applied into the electrolysis device comprises:
acquiring a preset electric quantity value Q applied to the electrolysis equipment when the output ratio of the carbon dioxide gas to the hydrogen is 1, and increasing nQ on the basis of the preset electric quantity value Q so as to adjust the output ratio of the carbon dioxide gas to the hydrogen; where n=1, 2,3, …, N (n.ltoreq.n).
10. The carbon dioxide capturing method according to claim 8, wherein in adjusting the production ratio of the carbon dioxide gas and the hydrogen gas, the carbon dioxide capturing method further comprises:
detecting the content of electrolyte in the electrolysis equipment in real time, and adding the electrolyte into the electrolysis equipment if the content of the electrolyte is smaller than a preset value; wherein the electrolyte is alkali metal sulfate, alkali metal nitrate alkali or alkali metal phosphate.
11. The method of claim 1, wherein the method of buffering the solution after the chemical reaction with the carbon dioxide gas by the buffer structure comprises:
setting at least two buffer structures for switching operation, wherein each buffer structure can selectively buffer the solution after the chemical reaction with the carbon dioxide gas is completed; and if the carbonate concentration in one buffer structure reaches a preset concentration value, deactivating the buffer structure, and activating the rest buffer structures.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211182959.2A CN117819550A (en) | 2022-09-27 | 2022-09-27 | Carbon dioxide capture methods |
| JP2025502696A JP2025524289A (en) | 2022-07-18 | 2022-10-21 | Carbon dioxide capture method and gas absorption system |
| PCT/CN2022/126781 WO2024016502A1 (en) | 2022-07-18 | 2022-10-21 | Carbon dioxide trapping method and gas absorption system |
| EP22951766.9A EP4494744A4 (en) | 2022-07-18 | 2022-10-21 | CARBON DIOXIDE CAPTURE PROCESS AND GAS ABSORPTION SYSTEM |
| CA3249802A CA3249802A1 (en) | 2022-07-18 | 2022-10-21 | Method for capturing carbon dioxide and gas absorption system |
| KR1020257002770A KR20250034409A (en) | 2022-07-18 | 2022-10-21 | Carbon dioxide capture method and gas absorption system |
| US18/900,845 US20250018329A1 (en) | 2022-07-18 | 2024-09-29 | Method for capturing carbon dioxide and gas absorption system |
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| US4049519A (en) * | 1976-10-06 | 1977-09-20 | Walter John Sloan | Carbonate reduction |
| CN101242885A (en) * | 2005-07-28 | 2008-08-13 | 环球研究技术有限公司 | remove carbon dioxide from the air |
| JP2008100211A (en) * | 2006-09-21 | 2008-05-01 | Yukio Yanagisawa | Mixed gas separation method and system |
| CN111257501A (en) * | 2020-01-20 | 2020-06-09 | 昆明瀚创科技有限公司 | Method for measuring concentration of hydroxyl in zinc sulfate solution |
| CN113439071A (en) * | 2020-01-22 | 2021-09-24 | 反町健司 | Method for fixing carbon dioxide, method for producing fixed carbon dioxide, and device for fixing carbon dioxide |
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