Measurement method of heat of reaction of the carbon dioxide absorbent and measurement of same

Abstract

A method and apparatus for measuring the reaction heat of a carbon dioxide absorbent are disclosed. The method for measuring the reaction heat of a carbon dioxide absorbent according to the present invention comprises: (a) a step of bringing a reactor into which an absorbent is introduced into contact with a fluid maintained at a first fluid temperature so that the absorbent has a first absorbent temperature; (b) a step of introducing a mixed gas containing carbon dioxide (CO2) into the reactor in contact with the fluid and causing an exothermic reaction to absorb the carbon dioxide into the absorbent; (c) a step of determining the area of ​​the exothermic section (△T) according to the exothermic reaction time of the absorbent until the carbon dioxide is saturated in the absorbent and the absorbent reaches the first absorbent temperature; and (d) a step of measuring the reaction heat (ΔH) of the carbon dioxide absorption reaction using the area of ​​the exothermic section (△T) of the absorbent. The method and apparatus for measuring the reaction heat of a carbon dioxide absorbent according to the present invention have the effect of selecting an absorbent that is easy to regenerate by selecting an absorbent with low heat of removal, and the apparatus for measuring the reaction heat of a carbon dioxide absorbent according to the present invention is economical and simple, and has the effect of solving the problem of heat loss and reaction heat measurement results that vary significantly depending on the measuring device.

Description

Technology Field

[0001] The present invention relates to a method for measuring the reaction heat of a carbon dioxide absorbent and a measuring device. Background Technology

[0002] Among technologies for reducing carbon dioxide (CO2) emitted from industrial flue gas, post-combustion CO2 capture technology using aqueous amine solutions is promising. Since the reaction between an aqueous amine solution and CO2 is reversible, applying heat to the absorbent removes CO2, allowing the absorbent to be reused. While the regeneration of the absorbent is essential for increasing process efficiency, renewable energy accounts for approximately 70% of the total process operating costs, significantly impacting the economic viability of the process. Therefore, researchers are focusing on developing absorbents that exhibit excellent reactivity with CO2 while consuming low renewable energy.

[0003] The regeneration energy of an absorbent consists of the sum of sensible heat, latent heat of vaporization, and heat of desorption; among these, heat of desorption is an important factor, accounting for approximately 40–50% of the regeneration energy. Therefore, selecting an absorbent with low heat of desorption is one method for selecting an absorbent that is easy to regenerate. Since the reaction between an aqueous amine solution and CO2 is a reversible reaction, the heat of desorption can be predicted using the heat of reaction of the absorbent. Conventional methods for measuring the heat of reaction have the disadvantage of high uncertainty in the measuring instrument (significant differences between instruments and heat loss issues) and high costs for equipment construction. The problem to be solved

[0004] The objective of the present invention is to provide a method for measuring the reaction heat of a carbon dioxide (CO2) absorbent by measuring the temperature change of the carbon dioxide absorbent.

[0005] In addition, another objective of the present invention is to provide an economical and simple device for measuring the reaction heat of a carbon dioxide (CO2) absorbent.

[0006] In addition, another objective of the present invention is to provide a method for selecting an absorbent that is easy to regenerate by utilizing the reaction heat of the absorbent. means of solving the problem

[0007] According to one aspect of the present invention, a method for measuring the reaction heat of a carbon dioxide absorbent is provided, comprising: (a) a step of bringing a reactor into which an absorbent is introduced into contact with a fluid maintained at a first fluid temperature so that the absorbent has a first absorbent temperature; (b) a step of introducing a mixed gas having carbon dioxide (CO2) into the reactor in contact with the fluid and causing an exothermic reaction to absorb the carbon dioxide into the absorbent; (c) a step of determining the exothermic section area (△T) according to the exothermic reaction time of the absorbent until the carbon dioxide is saturated in the absorbent and the absorbent reaches the first absorbent temperature; and (d) a step of measuring the reaction heat (ΔH) of the carbon dioxide absorption reaction using the exothermic section area (△T) of the absorbent.

[0008] In addition, the heat generation section area (△T) of the above absorbent can be calculated using the following Equation 1.

[0009] [Equation 1]

[0010]

[0011] In the above Equation 1

[0012] T is the temperature of the absorbent (°C), and

[0013] T0 is the first absorbent temperature (°C), which is the initial temperature of the absorbent, and

[0014] t exo is the exothermic reaction time (min) of the absorbent.

[0015] In addition, the above reaction heat (ΔH) can be calculated using the following Equation 2.

[0016] [Equation 2]

[0017]

[0018] In the above Equation 2

[0019] m is the mass (kg) of the added absorbent, and

[0020] C p ε is the specific heat capacity at constant pressure (kJ / kg·℃) of the CO2-fresh absorbent, and

[0021] △T is the area of ​​the exothermic region of the absorbent (min·℃), and

[0022] a and b are constants.

[0023] In addition, the above reaction heat (ΔH) can be calculated using the following Equation 3.

[0024] [Equation 3]

[0025]

[0026] In the above Equation 3

[0027] m is the mass (kg) of the added absorbent, and

[0028] C p is the constant-pressure specific heat (kJ / kg·℃) of the CO2-fresh absorbent, and

[0029] △T is the area of ​​the heat generation section (min·℃), and

[0030] a, b, and c are each constants.

[0031] In addition, the above reaction heat (ΔH) can be calculated using the following Equation 4.

[0032] [Equation 4]

[0033]

[0034] In the above Equation 4

[0035] m is the mass (kg) of the added absorbent, and

[0036] C p is the constant-pressure specific heat (kJ / kg·℃) of the CO2-fresh absorbent, and

[0037] △T is the area of ​​the heat generation section (min·℃), and

[0038] N CO2 is the amount of carbon dioxide absorbed (mol), and

[0039] a and b are constants.

[0040] In addition, the above reaction heat (ΔH) can be calculated using the following Equation 5.

[0041] [Equation 5]

[0042]

[0043] In Equation 5 above

[0044] m is the mass (kg) of the added absorbent, and

[0045] C p is the constant-pressure specific heat (kJ / kg·℃) of the CO2-fresh absorbent, and

[0046] △T is the area of ​​the heat generation section (min·℃), and

[0047] t exo is the exothermic reaction time (min) of the absorbent, and

[0048] N CO2 is the amount of carbon dioxide absorbed (mol), and

[0049] a, b, and c are each constants.

[0050] Additionally, step (a) may include (a-1) a step of positioning a reactor into which an absorbent has been introduced so as to be in contact with a fluid bath (220); and (a-2) a step of maintaining the fluid bath (220) at a first fluid temperature so that the absorbent has a first absorbent temperature.

[0051] Additionally, step (c) may include: (c-1) a step in which the carbon dioxide of the mixed gas reacts exothermically with the absorbent to increase the temperature of the absorbent; (c-2) a step in which the carbon dioxide saturates the absorbent and the temperature of the absorbent decreases due to contact between the reactor (210) and the fluid bath (220) to become the temperature of the first absorbent; and (c-3) a step of determining the exothermic section area (△T) according to the exothermic reaction time of the absorbent.

[0052] In addition, the area of ​​the exothermic region (△T) according to the exothermic reaction time of the absorbent may be a unique characteristic of the absorbent that varies depending on the absorbent.

[0053] In addition, the above absorbent is monoethanolamine (MEA), 1-amino-2-propanol (1A2P), 2-amino-1-butanol (2A1B), 2-amino-2-methyl-1-propanol (AMP), 2-(methylamino)ethanol (MAE), 2-(ethylamino)ethanol (EAE), 2-(butylamino)ethanol (BAE), 2-(isopropylamino)ethanol (IPAE), N-methyldiethanolamine (MDEA), 2-(dimethylamino)ethanol (DMAE), It may include one or more selected from the group consisting of 1-dimethylamino-2-propanol (1DMA2P), 1-piperidineethanol (1-PE), N,N-diethylethanolamine (N,N-diethylethanolamine, DEEA), 2-methylpiperazine (2MPZ), 2-(2-aminoethylamino)ethanol (2-(2-aminoethylamino)ethanol, AEEA), and N,N-dimethyl-1,3-propanediamine (N,N-dimethyl-1,3-propanediamine, DMPDA).

[0054] According to another aspect of the present invention, a reaction heat measuring device (10) for a carbon dioxide absorbent is provided, comprising: a mixed gas supply unit (100) including a mixed gas supply unit (110) that supplies a mixed gas containing carbon dioxide to a reactor (210); a reactor (210) that includes an absorbent, receives the mixed gas from the mixed gas supply unit (100), causes an exothermic reaction to absorb the mixed gas into the absorbent, and generates an exhaust gas, and a reaction unit (200) that contacts the reactor and maintains the temperature of the reactor at a predetermined temperature; a temperature measuring unit (300) including a temperature measuring device (310) that measures the temperature of the absorbent in the reactor (210) according to the exothermic reaction time; and an analysis unit (400) that receives the exhaust gas from the reaction unit (200) and analyzes the carbon dioxide content.

[0055] In addition, the reaction unit (200) may further include a condenser (230) that prevents the volatilization of the absorbent.

[0056] In addition, the above mixed gas analysis unit (400) may additionally include an exhaust gas dryer (Dryer, 420) and a vent (Vent, 403).

[0057] In addition, the exothermic region area (△T) of the above absorbent can be measured by the reaction heat measurement method.

[0058] In addition, the reaction heat (ΔH) of the above absorbent can be measured by the above reaction heat measurement method. Effects of the invention

[0059] The method for measuring the reaction heat of a carbon dioxide absorbent according to the present invention allows for the selection of an absorbent with low heat of removal, thereby having the effect of selecting an absorbent that is efficient and easy to regenerate.

[0060] In addition, the reaction heat measuring device of the carbon dioxide absorbent of the present invention is economical and simple, and has the effect of solving the problem of heat loss and reaction heat measurement results that vary greatly depending on the measuring device. Brief explanation of the drawing

[0061] These drawings are for reference to explain exemplary embodiments of the present invention, and therefore, the technical concept of the present invention should not be interpreted as being limited to the attached drawings. FIG. 1 is a flowchart showing the process of measuring the reaction heat of a carbon dioxide absorbent according to one embodiment of the present invention. FIG. 2 is a schematic diagram showing a reaction heat measuring device for a carbon dioxide absorbent according to one embodiment of the present invention. Figure 3 is a graph of the temperature measurement results of a carbon dioxide absorbent according to one embodiment of the present invention. FIG. 4 is a reaction heat (△H according to Equation 2, which is one embodiment of the present invention. predicted ) and literature values ​​(△H experimental This is a graph comparing the reaction heat of ). FIG. 5 is a reaction heat (△H according to Equation 3, which is one embodiment of the present invention. predicted ) and literature values ​​(△H experimental This is a graph comparing the reaction heat of ). FIG. 6 is a reaction heat (△H according to Equation 4, which is one embodiment of the present invention. predicted ) and literature values ​​(△H experimental This is a graph comparing the reaction heat of ). FIG. 7 is a reaction heat (△H according to Equation 5, which is one embodiment of the present invention. predicted ) and literature values ​​(△H experimental This is a graph comparing the reaction heat of ). Specific details for implementing the invention

[0062] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention.

[0063] However, the following description is not intended to limit the present invention to specific embodiments, and detailed descriptions of related prior art are omitted if it is determined that such detailed descriptions could obscure the essence of the present invention.

[0064] The terms used herein are merely for describing specific embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, terms such as “comprising” or “having” are intended to specify the presence of the features, numbers, steps, actions, components, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, or combinations thereof.

[0065] Additionally, terms including ordinal numbers, such as "first," "second," etc., used below may be used to describe various components, but said components are not limited by said terms. These terms are used solely for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be named the second component, and similarly, the second component may be named the first component.

[0066] Furthermore, when it is stated that a component is "formed" or "laminated" on another component, it should be understood that while it may be formed or laminated by being directly attached to the entire surface or one surface of the other component, there may also be other components present in between.

[0067] Hereinafter, the method and apparatus for measuring the reaction heat of a carbon dioxide absorbent according to the present invention will be described in detail. However, this is presented as an example and is not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0069] According to one aspect of the present invention, a method for measuring the reaction heat of a carbon dioxide absorbent is provided, comprising: (a) a step of bringing a reactor into which an absorbent is introduced into contact with a fluid maintained at a first fluid temperature so that the absorbent has a first absorbent temperature; (b) a step of introducing a mixed gas having carbon dioxide (CO2) into the reactor in contact with the fluid and causing an exothermic reaction to absorb the carbon dioxide into the absorbent; (c) a step of determining the exothermic section area (△T) according to the exothermic reaction time of the absorbent until the carbon dioxide is saturated in the absorbent and the absorbent reaches the first absorbent temperature; and (d) a step of measuring the reaction heat (ΔH) of the carbon dioxide absorption reaction using the exothermic section area (△T) of the absorbent.

[0070] In addition, the heat generation section area (△T) of the above absorbent can be calculated using the following Equation 1.

[0071] [Equation 1]

[0072]

[0073] In the above Equation 1

[0074] T is the temperature of the absorbent (°C), T0 is the first absorbent temperature (°C), which is the initial temperature of the absorbent, and t exo is the exothermic reaction time (min) of the absorbent.

[0075] In addition, the above reaction heat (ΔH) can be calculated using the following Equation 2.

[0076] [Equation 2]

[0077]

[0078] In the above Equation 2

[0079] m is the mass of the added absorbent (kg), and C p ε is the specific heat capacity at constant pressure (kJ / kg·°C) of the CO2-fresh absorbent, △T is the area of ​​the exothermic region (min·°C), and a and b are constants.

[0080] In addition, the above reaction heat (ΔH) can be calculated using the following Equation 3.

[0081] [Equation 3]

[0082]

[0083] In the above Equation 3

[0084] m is the mass of the added absorbent (kg), and C p ε₀ is the specific heat at constant pressure of the CO2-fresh absorbent (kJ / kg·°C), △T is the area of ​​the exothermic region (min·°C), and a, b, and c are each constants.

[0085] In addition, the above reaction heat (ΔH) can be calculated using the following Equation 4.

[0086] [Equation 4]

[0087]

[0088] In the above Equation 4

[0089] m is the mass of the added absorbent (kg), and C p ε is the constant-pressure specific heat (kJ / kg·°C) of the CO2-fresh absorbent, △T is the area of ​​the exothermic region (min·°C), and N CO2 is the amount of carbon dioxide absorbed (mol), and a and b are constants.

[0090] In addition, the above reaction heat (ΔH) can be calculated using the following Equation 5.

[0091] [Equation 5]

[0092]

[0093] In Equation 5 above

[0094] m is the mass of the added absorbent (kg), and C p ε is the constant-pressure specific heat (kJ / kg·°C) of the CO2-fresh absorbent, △T is the area of ​​the exothermic region (min·°C), and t exo is the exothermic reaction time (min) of the absorbent, and N CO2 ε is the amount of carbon dioxide absorbed (mol), and a, b, and c are each constants.

[0095] Additionally, step (a) may include (a-1) a step of positioning a reactor into which an absorbent has been introduced so as to be in contact with a fluid bath (220); and (a-2) a step of maintaining the fluid bath (220) at a first fluid temperature so that the absorbent has a first absorbent temperature.

[0096] Step (c) may include: (c-1) a step in which the carbon dioxide of the mixed gas reacts exothermically with the absorbent to increase the temperature of the absorbent; (c-2) a step in which the carbon dioxide saturates the absorbent and the temperature of the absorbent decreases due to contact between the reactor (210) and the fluid bath (220) to become the temperature of the first absorbent; and (c-3) a step of determining the exothermic section area (△T) according to the exothermic reaction time of the absorbent.

[0097] In addition, the area of ​​the exothermic region (△T) according to the exothermic reaction time of the absorbent may be a unique characteristic of the absorbent that varies depending on the absorbent.

[0098] In addition, the above absorbent is monoethanolamine (MEA), 1-amino-2-propanol (1A2P), 2-amino-1-butanol (2A1B), 2-amino-2-methyl-1-propanol (AMP), 2-(methylamino)ethanol (MAE), 2-(ethylamino)ethanol (EAE), 2-(butylamino)ethanol (BAE), 2-(isopropylamino)ethanol (IPAE), N-methyldiethanolamine (MDEA), 2-(dimethylamino)ethanol (DMAE), It may include one or more selected from the group consisting of 1-dimethylamino-2-propanol (1DMA2P), 1-piperidineethanol (1-PE), N,N-diethylethanolamine (N,N-diethylethanolamine, DEEA), 2-methylpiperazine (2MPZ), 2-(2-aminoethylamino)ethanol (2-(2-aminoethylamino)ethanol, AEEA), and N,N-dimethyl-1,3-propanediamine (N,N-dimethyl-1,3-propanediamine, DMPDA).

[0099] According to another aspect of the present invention, a reaction heat measuring device (10) for a carbon dioxide absorbent is provided, comprising: a mixed gas supply unit (100) including a mixed gas supply unit (110) that supplies a mixed gas containing carbon dioxide to a reactor (210); a reactor (210) that includes an absorbent, receives the mixed gas from the mixed gas supply unit (100), causes an exothermic reaction to absorb the mixed gas into the absorbent, and generates an exhaust gas, and a reaction unit (200) that contacts the reactor and maintains the temperature of the reactor at a predetermined temperature, and a fluid bath (220); a temperature measuring unit (300) that includes a temperature measuring unit (310) that measures the temperature of the absorbent in the reactor (210) according to the exothermic reaction time; and an analysis unit (400) that includes an analyzer (410) that receives the exhaust gas from the reaction unit (200) and analyzes the carbon dioxide content.

[0100] In addition, the reaction unit (200) may further include a condenser (230) that prevents the volatilization of the absorbent.

[0101] In addition, the above mixed gas analysis unit (400) may additionally include an exhaust gas dryer (Dryer, 420) and a vent (Vent, 403).

[0102] In addition, the exothermic region area (△T) of the above absorbent can be measured by the reaction heat measurement method.

[0103] In addition, the reaction heat (ΔH) of the above absorbent can be measured by the above reaction heat measurement method.

[0105] [Example]

[0106] Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only and does not limit the scope of the present invention.

[0108] 1. Construction of a carbon dioxide absorbent reaction heat measuring device

[0109] FIG. 1 is a flowchart showing the process of measuring the reaction heat of a carbon dioxide absorbent according to one embodiment of the present invention, and FIG. 2 is a schematic diagram showing a carbon dioxide absorbent reaction heat measuring device according to one embodiment of the present invention.

[0110] Referring to FIGS. 1 and 2, a carbon dioxide absorbent reaction heat measuring device according to one embodiment of the present invention includes a mixed gas supply unit (100), a reaction unit (200), a temperature measuring unit (300), and an analysis unit (400).

[0111] The above mixed gas supply unit (100) includes a mixed gas supply unit (110), a mass flow rate controller (MFC, 120), and a gas mixer (130). The above reaction unit (200) includes a reactor (210), a fluid bath (220), a condenser (230), a gas disperser (240), and a purging line (250), and the temperature measuring unit (300) includes a temperature measuring device (310) that measures the temperature of the absorbent in the reactor (210) according to the exothermic reaction time. The above analysis unit (400) includes an analyzer (410), a dryer (420), and a vent (403) to receive exhaust gas from the reactor (210) and analyze the carbon dioxide content.

[0113] 2. Conduct carbon dioxide absorption reaction of the carbon dioxide absorbent

[0114] The concentration of the gas used in the experiment was 15% CO2 (N2 balance), which is the flue gas of a coal-fired power plant, using a flow controller (120), and a reactor (210) containing 100 g of absorbent was placed in a fluid bath (230) preheated to 43 ℃ before the start of the experiment to carbon dioxide The temperature of the absorbent was maintained at 40 ℃ before absorption. At this time, a reactor with a diameter of 7 cm, a height of 7.8 cm, and a thickness of 0.2 cm was used.

[0115] When the temperature of the absorbent reaches 40 ℃, 15% CO2 (N2 balance) is injected into the reactor (210) at a rate of 2 L / min to cause an exothermic reaction in the carbon dioxide absorbent.

[0116] The temperature of the absorbent and the carbon dioxide concentration at the outlet were measured during the exothermic reaction.

[0118] 3. Derivation of the equation for measuring the reaction heat of carbon dioxide absorbent

[0119] 3-1. Calculation of the Exothermic Section Area (△T) of the Carbon Dioxide Absorbent

[0120] Using temperature data of the carbon dioxide absorbent measured during the absorption reaction, the area of ​​the exothermic region (△T) of the carbon dioxide absorbent, which is a factor used in calculating the heat of reaction, can be calculated.

[0121] Figure 3 is a graph of the temperature measurement results of a carbon dioxide absorbent according to one embodiment of the present invention.

[0122] Since the reaction between the amine aqueous solution absorbent and carbon dioxide is an exothermic reaction, the temperature of the absorbent rises rapidly at the beginning of absorption and tends to gradually approach 40°C as the absorbent becomes saturated with carbon dioxide; this is a unique value that varies depending on the absorbent. Using Equation 1, the degree of exothermic reaction due to carbon dioxide absorption was quantified by integrating based on an initial temperature of 40°C, and this value was defined as the area of ​​the exothermic region (△T) of the carbon dioxide absorbent.

[0123] [Equation 1]

[0124]

[0125] In the above Equation 1, T is the temperature of the absorbent (°C), T0 is the first absorbent temperature (°C), which is the initial temperature of the absorbent, and t exo is the exothermic reaction time (min) of the absorbent.

[0127] Also, the specific heat of the absorbent (C p) was measured using Differential Scanning Calorimetry (DSC) at an absorption temperature of 40 ℃.

[0129] 3-2. Derivation of the Equation for Measuring the Heat of Reaction of Carbon Dioxide Absorbent

[0130] The calculation of the reaction heat of a basic carbon dioxide absorbent is a thermodynamic formula It is based on. Assuming that the specific heat of the absorbent is constant during the absorption reaction and introducing a correction constant, the heat of reaction of the absorbent can be calculated using Equation 2.

[0131] [Equation 2]

[0132]

[0133] In Equation 2 above, m is the mass (kg) of the added absorbent, and C p ε is the specific heat capacity at constant pressure (kJ / kg·°C) of the CO2-fresh absorbent, △T is the area of ​​the exothermic region (min·°C), and a and b are constants.

[0135] Since the carbon dioxide absorbent reaction heat measuring device is not in an adiabatic state, heat loss occurs during the reaction heat measurement. Therefore, in Equation 2, the heat of the carbon dioxide absorbent (mC p △T) and exothermic reaction time (t exo Equation 3 was derived by introducing a heat loss correction term proportional to ).

[0136] [Equation 3]

[0137]

[0138] In Equation 3 above, m is the mass (kg) of the added absorbent, and C p ε₀ is the specific heat at constant pressure of the CO2-fresh absorbent (kJ / kg·°C), △T is the area of ​​the exothermic region (min·°C), and a, b, and c are each constants.

[0140] Since the reaction heat of a carbon dioxide absorbent is the reaction heat per amount of carbon dioxide absorbed, the amount of carbon dioxide absorbed (N) in Equations 2 and 3 CO2 Equations 4 and 5 were derived by dividing ).

[0141] [Equation 4]

[0142]

[0143] In Equation 4 above, m is the mass (kg) of the added absorbent, and C p ε is the constant-pressure specific heat (kJ / kg·°C) of the CO2-fresh absorbent at 40°C, △T is the area of ​​the exothermic region (min·°C), and N CO2 is the amount of carbon dioxide absorbed (mol), and a and b are constants.

[0145] In the above Equation 4, the total heat loss of the reactor (210) is the heat of the absorbent (mC p △T) and exothermic reaction time (t exo Equation 5 was derived by introducing a heat loss correction term proportional to ).

[0146] [Equation 5]

[0147]

[0148] In Equation 5 above, m is the mass (kg) of the added absorbent, and C p ε is the constant-pressure specific heat (kJ / kg·°C) of the CO2-fresh absorbent at 40°C, △T is the area of ​​the exothermic region (min·°C), and t exo is the exothermic reaction time (min) of the absorbent, and N CO2 ε is the amount of carbon dioxide absorbed (mol), and a, b, and c are each constants.

[0150] 4. Measurement of the reaction heat of carbon dioxide absorbent

[0151] 4-1. Specific heat of carbon dioxide absorbent (C p ), area of ​​the heat generation section (△T) and exothermic reaction time (t exo ) Derived result

[0152] FIG. 2 is a schematic diagram showing a carbon dioxide absorbent reaction heat measuring device according to one embodiment of the present invention, and FIG. 3 is a graph of the temperature measurement results of a carbon dioxide absorbent according to one embodiment of the present invention.

[0153] The area of ​​the exothermic region (ΔT) of the absorbent was calculated according to Equation 1 above, and also the specific heat (C) of the absorbent p ) was measured using Differential Scanning Calorimetry (DSC) at an absorption temperature of 40 ℃. Here, the initial temperature of the carbon dioxide absorbent was 40 ℃, and the temperature of the fluid in the fluid bath was maintained at 43 ℃. The temperature of the absorbent rose due to the exothermic reaction of carbon dioxide absorption, then decreased and was maintained at 40 ℃. It was determined that the reason the temperature of the absorbent did not converge to the temperature of the fluid in the fluid bath after the carbon dioxide absorption reaction was due to heat loss to the surface of the reactor that was not in contact with the fluid.

[0154] Specific heat of carbon dioxide absorbent (C p ), area of ​​the heat generation section (△T) and exothermic reaction time (t exo The results of the calculation are as shown in Table 1 below.

[0156] turn absorbent Molar concentration (mol / L) Specific heat at 40 ℃ (C p, kJ / kg·℃) Area of ​​the heat generation section (△T, min·℃) Exothermic reaction time (t exo , min) 1 MEA 4.912 3.935 166.6 76.0 2 1A2P 3.994 4.019 131.8 42.5 3 2A1B 3.365 3.932 118.3 40.5 4 AMP 3.365 3.922 111.2 107.0 5 MAE 3.994 4.028 114.0 35.5 6 EAE 3.365 3.729 112.2 40.0 7 BAE 2.560 3.664 88.1 34.7 8 IPAE 2.908 3.584 70.8 84.7 9 MDEA 2.518 3.658 19.8 70.8 10 DMAE 3.365 3.941 39.5 51.2 11 1DMA2P 2.908 3.994 41.1 101.8 12 1-PE 2.322 3.895 35.7 65.3 13 DEEA 2.560 4.271 23.8 75.3 14 2MPZ 2.995 3.814 140.7 58.8 15 AEEA 2.880 3.938 175.5 47.8 16 DMPDA 2.936 4.288 184.7 98.8

[0157] Here, MEA is monoethanolamine, 1A2P is 1-amino-2-propanol, 2A1B is 2-amino-1-butanol, AMP is 2-amino-2-methyl-1-propanol, MAE is 2-(methylamino)ethanol, EAE is 2-(ethylamino)ethanol, BAE is 2-(butylamino)ethanol, IPAE is 2-(isopropylamino)ethanol, MDEA is N-methyldiethanolamine, DMAE is 2-(dimethylamino)ethanol, and 1DMA2P is 1-dimethylamino-2-propanol, 1-PE is 1-piperidineethanol, DEEA is N,N-diethylethanolamine, 2MPZ is 2-methylpiperazine, AEEA is 2-(2-aminoethylamino)ethanol, and DMPDA is N,N-dimethyl-1,3-propanediamine.

[0159] 4-2. Calculation Results of Reaction Heat of Carbon Dioxide Absorbent

[0160] 1) Heat of reaction according to Equation 2 (△H predicted ) Calculation result

[0161] FIG. 4 is a reaction heat (△H according to Equation 2, which is one embodiment of the present invention. predicted ) and literature values ​​(△H experimental This is a graph comparing the reaction heats of ), and Table 2 below shows the reaction heat (△H according to Equation 2. predicted ) and literature values ​​(△H experimental It is the comparison value of ).

[0162] Referring to Figure 4 and Table 2, the experimental results of the heat of reaction according to Equation 2 and the literature value of the heat of reaction (△H experimental As a result of regression analysis, the constant a was derived as -0.48349 and the constant b as -55.33364. The heat of reaction (△H according to Equation 2 predicted ) and literature values ​​(△H experimental Consistency with ) was confirmed by AAD% (Average Absolute Deviation). The AAD% of Equation 3 was 2.7693%, showing a low error range. Therefore, it was confirmed that the heat of reaction can be measured simply and accurately using the measuring device and method of the present invention.

[0163] turn absorbent Molar concentration (mol / L) Heat of reaction (kJ / mol CO2) Literature value (△H experimental ) Document number Reaction heat according to Equation 2 (△H predicted ) 1 MEA 4.912 -86.90 1 -87.03 2 1A2P 3.994 -85.47 2 -80.94 3 2A1B 3.365 -82.49 2 -77.82 4 AMP 3.365 -80.91 2 -76.42 5 MAE 3.994 -73.84 2 -77.53 6 EAE 3.365 -78.04 3 -75.56 7 BAE 2.560 -74.38 2 -70.94 8 IPAE 2.908 -63.5 1 -67.60 9 MDEA 2.518 -58.50 4 -58.84 10 DMAE 3.365 -63.26 2 -62.86 11 1DMA2P 2.908 -60.72 2 -63.27 12 1-PE 2.322 -58.2 4 -62.06 13 DEEA 2.560 -62.4 4 -60.25 14 2MPZ 2.995 -79.65 5 -81.28 15 AEEA 2.880 -85.18 6 -88.75 16 DMPDA 2.936 -91.33 2 -93.62

[0164] In Tables 2 to 9, Reference 1: Energy Procedia 4 (2011) 201-208, Reference 2: Applied Energy 185 (2017) 1433-1449, Reference 3: Industrial & Engineering Chemistry Research 59(8) (2020) 3475-3484, Reference 4: Industrial & Engineering Chemistry Research 52(24) (2013) 8323-8331, Reference 5: Choi Jeong-ho et al., Journal of the Korean Hydrogen & New Energy Society (2018), Reference 6: Industrial & Engineering Chemistry Research 46(17) (2007) 5803-5809.

[0166] 2) Heat of reaction according to Equation 3 (△H predicted ) Calculation result

[0167] FIG. 5 is a reaction heat (△H according to Equation 3, which is one embodiment of the present invention. predicted ) and literature values ​​(△H experimental This is a graph comparing the reaction heats of ), and Table 3 below shows the reaction heat (△H) according to Equation 3. predicted) and literature values ​​(△H experimental This is the reaction heat comparison value of ).

[0168] Referring to Fig. 5 and Table 3, the experimental results of the heat of reaction according to Equation 3 and the literature value of the heat of reaction (△H experimental As a result of regression analysis, the constant a was derived as -0.51386, the constant b as 0.00043, and the constant c as -55.21204. The AAD% of Equation 3 was 2.6764%, showing higher accuracy than Equation 2 (2.7693%).

[0169] turn absorbent Molar concentration (mol / L) Heat of reaction (kJ / mol CO2) Literature value (△H experimental ) Document number Reaction heat (△H according to Equation 3 predicted ) 1 MEA 4.912 -86.90 1 -86.76 2 1A2P 3.994 -85.47 2 -81.46 3 2A1B 3.365 -82.49 2 -78.31 4 AMP 3.365 -80.91 2 -75.62 5 MAE 3.994 -73.84 2 -78.11 6 EAE 3.365 -78.04 3 -75.99 7 BAE 2.560 -74.38 2 -71.32 8 IPAE 2.908 -63.5 1 -67.33 9 MDEA 2.518 -58.50 4 -58.71 10 DMAE 3.365 -63.26 2 -62.87 11 1DMA2P 2.908 -60.72 2 -62.93 12 1-PE 2.322 -58.2 4 -61.97 13 DEEA 2.560 -62.4 4 -60.11 14 2MPZ 2.995 -79.65 5 -81.43 15 AEEA 2.880 -85.18 6 -89.31 16 DMPDA 2.936 -91.33 2 -92.55

[0170] 3) Heat of reaction according to Equation 4 (△H predicted ) Calculation result

[0171] FIG. 6 is a reaction heat (△H according to Equation 4, which is one embodiment of the present invention. predicted ) and literature values ​​(△H experimental This is a comparison graph of the experimental results for measuring the heat of reaction of ), and Table 4 below shows the heat of reaction (△H) according to Equation 4. predicted ) and literature values ​​(△H experimental It is the comparison value of ).

[0172] Referring to Fig. 6 and Table 4, the experimental results of the heat of reaction according to Equation 4 and the literature value of the heat of reaction (△H experimental As a result of regression analysis, the constant a was derived as -0.14648 and the constant b as -48.67995. The AAD% of Equation 4 was 2.4934%, showing higher accuracy than Equation 2 (2.7693%).

[0173] turn absorbent Molar concentration (mol / L) Heat of reaction (kJ / mol CO2) Literature value (△H experimental ) Document number Reaction heat (△H according to Equation 4 predicted ) 1 MEA 4.912 -86.90 1 -85.07 2 1A2P 3.994 -85.47 2 -84.99 3 2A1B 3.365 -82.49 2 -84.41 4 AMP 3.365 -80.91 2 -76.72 5 MAE 3.994 -73.84 2 -79.70 6 EAE 3.365 -78.04 3 -77.64 7 BAE 2.560 -74.38 2 -77.53 8 IPAE 2.908 -63.5 1 -66.08 9 MDEA 2.518 -58.50 4 -59.05 10 DMAE 3.365 -63.26 2 -60.85 11 1DMA2P 2.908 -60.72 2 -62.47 12 1-PE 2.322 -58.2 4 -62.34 13 DEEA 2.560 -62.4 4 -56.86 14 2MPZ 2.995 -79.65 5 -78.15 15 AEEA 2.880 -85.18 6 -85.04 16 DMPDA 2.936 -91.33 2 -87.87

[0174] 4) Heat of reaction according to Equation 5 (△H predicted ) Calculation result

[0175] FIG. 7 is a reaction heat (△H according to Equation 5, which is one embodiment of the present invention. predicted ) and literature values ​​(△H experimental This is a comparison graph of the experimental results for measuring the heat of reaction of ), and Table 5 below shows the heat of reaction (△H) according to Equation 5. predicted ) and literature values ​​(△H experimentalIt is the comparison value of ).

[0176] Referring to Fig. 7 and Table 5, the experimental results of the heat of reaction according to Equation 5 and the literature value of the heat of reaction (△H experimental As a result of regression analysis, the constant a was found to be -0.12800, the constant b was -0.00034, and the constant c was -48.2199. The AAD% of Equation 5 was 2.0825%, showing higher accuracy than Equation 3 (2.6764%) and Equation 4 (2.4934%).

[0178] turn absorbent Molar concentration (mol / L) Heat of reaction (kJ / mol CO2) Literature value (△H experimental ) Document number Reaction heat (△H according to Equation 5 predicted ) 1 MEA 4.912 -86.90 1 -86.47 2 1A2P 3.994 -85.47 2 -83.54 3 2A1B 3.365 -82.49 2 -82.82 4 AMP 3.365 -80.91 2 -79.72 5 MAE 3.994 -73.84 2 -77.90 6 EAE 3.365 -78.04 3 -76.23 7 BAE 2.560 -74.38 2 -75.76 8 IPAE 2.908 -63.5 1 -66.87 9 MDEA 2.518 -58.50 4 -58.99 10 DMAE 3.365 -63.26 2 -60.30 11 1DMA2P 2.908 -60.72 2 -63.55 12 1-PE 2.322 -58.2 4 -62.24 13 DEEA 2.560 -62.4 4 -56.80 14 2MPZ 2.995 -79.65 5 -78.02 15 AEEA 2.880 -85.18 6 -84.05 16 DMPDA 2.936 -91.33 2 -91.50 Explanation of the symbols

[0180] 10: Carbon dioxide absorbent reaction heat measuring device 110 : Mixed gas supply unit 120 : Mass flow rate controller (MFC) 130 : Gas Mixer 210 : Reactor 220 : Fluid bath 230 : Condenser 240 : Gas disperser 250 : Purging line 310 : Temperature gauge 410 : Analyzer 420 : Dryer 430 : Vent

Claims

Claim 1 (a) a step of bringing a reactor into which an absorbent has been introduced into contact with a fluid maintained at a first fluid temperature so that the absorbent has a first absorbent temperature; (b) a step of introducing a mixed gas containing carbon dioxide (CO2) into the reactor in contact with the fluid and causing an exothermic reaction to absorb the carbon dioxide into the absorbent; (c) a step of determining the area of ​​the exothermic section (△T) according to the exothermic reaction time of the absorbent until the carbon dioxide is saturated in the absorbent and the absorbent reaches the first absorbent temperature; and (d) a step of measuring the reaction heat (ΔH) of the carbon dioxide absorption reaction using the area of ​​the exothermic section (△T) of the absorbent; wherein the reaction heat (ΔH) is calculated using the following Equations 2, 3, 4, or 5. [Equation 2] In Equation 2 above, m is the mass (kg) of the added absorbent, and C p ε is the specific heat capacity at constant pressure (kJ / kg·°C) of the CO2-fresh absorbent, △T is the area of ​​the exothermic region (min·°C), a and b are constants, [Equation 3] In Equation 3 above, m is the mass (kg) of the added absorbent, and C p ε is the constant-pressure specific heat (kJ / kg·°C) of the CO2-fresh absorbent, △T is the area of ​​the exothermic region (min·°C), and t exo ε₀ is the exothermic reaction time (min) of the absorbent, and a, b, and c are each constants, [Equation 4] In Equation 4 above, m is the mass (kg) of the added absorbent, and C p ε is the constant-pressure specific heat (kJ / kg·°C) of the CO2-fresh absorbent, △T is the area of ​​the exothermic region (min·°C), and N CO2 ε₀ is the amount of carbon dioxide absorbed (mol), a and b are constants, [Equation 5] In Equation 5 above, m is the mass (kg) of the added absorbent, and C p ε is the constant-pressure specific heat (kJ / kg·°C) of the CO2-fresh absorbent, △T is the area of ​​the exothermic region (min·°C), and t exo is the exothermic reaction time (min) of the absorbent, and N CO2 ε is the amount of carbon dioxide absorbed (mol), and a, b, and c are each constants. Claim 2 A method for measuring the reaction heat of a carbon dioxide absorbent according to claim 1, characterized in that the area of ​​the exothermic section (△T) of the absorbent is calculated using the following Equation 1. [Equation 1] In the above Equation 1, T is the temperature of the absorbent (°C), T0 is the first absorbent temperature (°C), which is the initial temperature of the absorbent, and t exo is the exothermic reaction time (min) of the absorbent. Claim 3 delete Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 A method for measuring the reaction heat of a carbon dioxide absorbent according to claim 1, characterized in that step (a) comprises: (a-1) a step of positioning a reactor into which an absorbent has been introduced so as to be in contact with a fluid bath (220); and (a-2) a step of maintaining the fluid bath (220) at a first fluid temperature so that the absorbent has a first absorbent temperature. Claim 8 A method for measuring the reaction heat of a carbon dioxide absorbent according to claim 1, wherein step (c) comprises: (c-1) a step in which the carbon dioxide of the mixed gas reacts exothermically with the absorbent to increase the temperature of the absorbent; (c-2) a step in which the carbon dioxide saturates the absorbent and the temperature of the absorbent decreases due to contact between the reactor (210) and the fluid bath (220) to become the temperature of the first absorbent; and (c-3) a step of determining the area of ​​the exothermic section (△T) according to the exothermic reaction time of the absorbent. Claim 9 A method for measuring the reaction heat of a carbon dioxide absorbent according to claim 1, characterized in that the area of ​​the exothermic section (△T) according to the exothermic reaction time of the absorbent is an inherent characteristic of the absorbent that varies depending on the absorbent. Claim 10 In claim 1, the absorbent is monoethanolamine (MEA), 1-amino-2-propanol (1A2P), 2-amino-1-butanol (2A1B), 2-amino-2-methyl-1-propanol (AMP), 2-(methylamino)ethanol (MAE), 2-(ethylamino)ethanol (EAE), 2-(butylamino)ethanol (BAE), 2-(isopropylamino)ethanol (IPAE), N-methyldiethanolamine (MDEA), 2-(dimethylamino)ethanol (DMAE), A method for measuring the reaction heat of a carbon dioxide absorbent, characterized by comprising one or more selected from the group consisting of 1-dimethylamino-2-propanol (1DMA2P), 1-piperidineethanol (1-PE), N,N-diethylethanolamine (N,N-diethylethanolamine, DEEA), 2-methylpiperazine (2MPZ), 2-(2-aminoethylamino)ethanol (2-(2-aminoethylamino)ethanol, AEEA), and N,N-dimethyl-1,3-propanediamine (N,N-dimethyl-1,3-propanediamine, DMPDA). Claim 11 A reaction heat measuring device (10) for a carbon dioxide absorbent, comprising: a mixed gas supply unit (100) including a mixed gas supply unit (110) for supplying a mixed gas containing carbon dioxide to a reactor (210); a reactor (210) including an absorbent, which receives the mixed gas from the mixed gas supply unit (100), causes an exothermic reaction to absorb it into the absorbent, and generates an exhaust gas; a reaction unit (200) including a fluid bath (220) that contacts the reactor and maintains the temperature of the reactor at a predetermined temperature; a temperature measuring unit (300) including a temperature measuring device (310) for measuring the temperature of the absorbent in the reactor (210) according to the exothermic reaction time; and an analysis unit (400) including an analyzer (410) that receives the exhaust gas from the reaction unit (200) and analyzes the carbon dioxide content, wherein the reaction heat (ΔH) of the absorbent is measured by the reaction heat measuring method according to claim 1. Claim 12 A reaction heat measuring device for a carbon dioxide absorbent, characterized in that, in claim 11, the reaction unit (200) further includes a condenser (230) that prevents volatilization of the absorbent. Claim 13 A reaction heat measuring device for a carbon dioxide absorbent, characterized in that, in claim 11, the analysis unit (400) further includes an exhaust gas dryer (Dryer, 420) and a vent (Vent, 403). Claim 14 A reaction heat measuring device for a carbon dioxide absorbent, wherein, in claim 11, the area of ​​the heat-generating section (△T) of the absorbent is measured by the reaction heat measuring method according to claim 2. Claim 15 delete

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