WO2019212208A1 - Carbon dioxide absorbent comprising polyhydroxy amine-based polymer, catalyst for regenerating carbon dioxide absorbent, method for absorbing/isolating carbon dioxide by using same, and method for regenerating carbon dioxide absorbent - Google Patents

Abstract

The present invention relates to a carbon dioxide absorbent comprising a novel polyhydroxy amine-based polymer, a catalyst for regenerating the carbon dioxide absorbent, a method for absorbing/isolating carbon dioxide by using same, and a method for regenerating the carbon dioxide absorbent. The carbon dioxide absorbent comprising the polyhydroxy amine-based polymer produced by reacting an amine precursor, an aldehyde precursor, an ammonium halide, and the like, and the catalyst for regenerating the carbon dioxide absorbent according to one example of the present invention show desirable carbon dioxide absorption capacity and have significantly lower regeneration temperature than an existing alkanol amine-based absorbent, and thus, can significantly reduce the overall energy consumption required for a capture process, and furthermore, by virtue of the low regeneration temperature, can prevent the recovered carbon dioxide from being contaminated with moisture and absorbent vapors.

Description

Carbon dioxide absorbent comprising polyamine hydroxide polymer, catalyst for regenerating carbon dioxide absorbent, method for absorbing / separating carbon dioxide using the same, and regenerating carbon dioxide absorbent

The present invention relates to a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer, a catalyst for regenerating a carbon dioxide absorbent, a method for absorbing / separating carbon dioxide using the same, and a method for regenerating a carbon dioxide absorbent. More specifically, the present invention provides a carbon dioxide absorbent comprising a polyamine hydroxide polymer having excellent carbon dioxide absorption ability, absorption rate, and reproducibility, a catalyst for regenerating a carbon dioxide absorbent, a method for absorbing / separating carbon dioxide using the same, and a method for regenerating a carbon dioxide absorbent. It is about.

The most effective way to remove carbon dioxide from gases containing carbon dioxide, such as gas mixtures from hydrogen, steel and cement production processes, combustion flue gases from natural power plants and fossil fuels, and chemicals using amine-based aqueous solutions Absorption method. As the chemical absorbents, amine aqueous solutions such as monoethanolamine (MEA), diethanolamine (DEA), and the like have been studied the most, and these amine-based absorbents react with carbon dioxide to facilitate stable carbamate compounds. This is because these compounds are thermally decomposed into carbon dioxide and amine so that the alkanolamine absorbent can be regenerated. However, this process presents some serious problems, in particular the degradation of absorbents due to the generation and decomposition of by-products by impurities such as NOx, SOx, and oxygen contained in combustion exhaust gases, resulting in device corrosion problems, carbon dioxide and The high thermal and chemical stability of the carbamate resulting from the reaction caused by excessive regeneration energy consumption due to high regeneration temperature above 120 ° C., excessive volatilization loss of alkanolamine at high regeneration temperature, and thus sorbent replenishment problem, Due to the low vapor pressure of the absorbent, the problem of polluting the separated carbon dioxide during the regeneration process has been pointed out as a disadvantage.

In order to compensate for the disadvantages of the amine-based aqueous solution absorbents, methods of physically absorbing carbon dioxide using organic solvents such as selexol, IFPexol, and NFM have been reported. The most important advantage of organic solvent absorbents is that much lower energy is required for carbon dioxide recovery and solvent regeneration, since carbon dioxide absorption is achieved only by the physical interaction between the absorbing solvent and carbon dioxide rather than the chemical bonds as in amine-based aqueous solutions. In the case of using an aqueous amine-based absorbent, carbon dioxide recovery and absorbent regeneration require energy-intensive high temperature stripping, whereas in the case of physical absorption, carbon dioxide dissolved in the solvent simply by changing the pressure without increasing the temperature. Can be recovered.

However, when the physical absorbents separate the carbon dioxide from the combustion gas having a low pressure, the physical absorbents exhibit much lower carbon dioxide absorption than the amine absorbents, and thus, the circulation rate of the absorbent must be increased, thus requiring a larger equipment. Recently, new chemical absorbents having high thermal and chemical stability and low vapor pressure have been studied to overcome the disadvantages of the existing amine absorbents and organic solvent absorbents. In this regard, as a method of lowering the renewable energy of the chemical absorbent, a study has been attempted using an alkanolamine having a steric hindrance around the amine group of the alkanolamine as an absorbent. -Methyl-1-propanol (AMP). AMP has a 30% lower renewable energy than MEA because it forms a bicarbonate compound that is easier to regenerate than carbamate when carbon dioxide is reacted, but the carbon dioxide absorption rate is less than 50% of MEA. .

In order to increase the absorption rate of AMP, Mitsubishi Heavy Industries and Kansai Thermal Power Co., Ltd. jointly developed a new absorbent that added piperazine, a secondary cycloamine to AMP, and registered a patent (Japanese Patent No. 3197173). . However, the patent has a problem that precipitation occurs after carbon dioxide absorption due to the use of excess piperazine, and regeneration is difficult because piperazine and carbon dioxide react to form a carbamate, which is a stable compound in addition to bicarbonate.

In addition, transition metal oxide such as H-ZSM, γ-Al ₂ O ₃ , MoO ₃ , V ₂ O ₅ , TiO (OH) _2, etc. Literature using catalysts has been reported. These metal oxides reduce the heat duty for amine regeneration, thereby demonstrating the possibility of regeneration temperatures of 90-110 ° C., lower than conventional 120 ° C. However, it is still a problem to develop a catalyst that can be repeatedly and stably proceeded below 100 ℃.

An object of the present invention is to provide a carbon dioxide absorbent, a catalyst for regenerating a carbon dioxide absorbent, which has a high carbon dioxide absorbing ability and a highly durable polyhydroxyamine-based polymer capable of operating a carbon dioxide capture process under low regeneration temperature conditions in order to solve the above problems. It is to provide a method for absorbing / separating carbon dioxide and regenerating a carbon dioxide absorbent using the same.

In exemplary embodiments of the present invention, it provides a carbon dioxide absorbent comprising a polyhydroxylamine-based polymer represented by the following formula (1) or (2).

[Formula 1]

[Formula 2]

In the formulas (1) and (2), Halide is a halogen element and n is a repeating unit.

In exemplary embodiments of the present invention, a method for preparing a carbon dioxide absorbent including the aforementioned polyhydroxyamine-based polymer, comprising: reacting an amine compound, an aldehyde precursor, and an ammonium halide; comprising a polyhydroxyamine-based polymer It provides a method for producing a carbon dioxide absorbent.

In exemplary embodiments of the present invention, by using an aqueous solution containing a carbon dioxide absorbent comprising the polyhydroxylamine-based polymer described above, absorbing carbon dioxide provides a method for absorbing carbon dioxide.

In exemplary embodiments of the present invention, a first step of absorbing carbon dioxide from a gas mixture containing carbon dioxide by using an aqueous solution comprising a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer described above; And a second step of removing the carbon dioxide absorbed from the aqueous solution including the carbon dioxide absorbent including the polyhydroxyamine-based polymer.

Exemplary embodiments of the present invention provide a catalyst for regenerating a carbon dioxide absorbent including a polyhydroxyamine-based polymer represented by Formula 1 or Formula 2 below.

[Formula 1]

[Formula 2]

In the formulas (1) and (2), Halide is a halogen element and n is a repeating unit.

In exemplary embodiments of the present invention, there is provided a method for regenerating an amine-based carbon dioxide absorbent, the method comprising: absorbing carbon dioxide from a gas mixture including carbon dioxide using an aqueous solution including an amine-based carbon dioxide absorbent; And a second step of removing the carbon dioxide absorbed from the aqueous solution containing the amine-based carbon dioxide absorbent using the catalyst for regenerating the carbon dioxide absorbent including the polyhydroxyamine-based polymer described above. to provide.

According to the exemplary embodiment of the present invention, the carbon dioxide absorbent including the polyhydroxyamine-based polymer has a high carbon dioxide absorption capacity and a fast absorption rate, and has a significantly lower absorbent regeneration temperature than a conventional absorbent so that the total energy required for the absorption process is reduced. Consumption can be greatly reduced and the initial absorption capacity can be maintained almost even after repeated absorption / removal of carbon dioxide.

In addition, in the case of a catalyst for regenerating a carbon dioxide absorbent containing a polyhydroxyamine-based polymer, functional groups such as hydroxyl and amine groups on the surface of the polymer enable decomposition and regeneration of the carbamate compound at a low temperature, thereby significantly increasing the regeneration efficiency, thereby reducing carbon dioxide wet. The overall energy consumption of the capture process can be significantly reduced, and the initial absorption capacity can be stably maintained even after repeated carbon dioxide absorption and stripping.

In addition, according to one embodiment of the present invention, it is possible to significantly reduce the overall energy consumption, so that the cost saving effect is expected, it can be applied to the entire industry that emits a large amount of carbon dioxide, synthesis of high value-added organic material using the collected carbon dioxide It is expected to be applicable to the field.

1 is an FT-IR spectrum of a carbon dioxide absorbent according to an embodiment of the present invention.

Figure 2 is a graph of carbon dioxide absorption according to the CO ₂ / N ₂ ratio (10% / 90% and 30% / 70%) of the carbon dioxide absorbent according to an embodiment of the present invention.

3 is a graph of carbon dioxide absorption / regeneration at 25/80 ° C. of a carbon dioxide absorbent according to an embodiment of the present invention.

Term Definition

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The embodiments of the present invention disclosed in the text are only illustrated for illustrative purposes, and the embodiments of the present invention may be embodied in various forms and should not be construed as being limited to the embodiments described in the text. .

The present invention may be modified in various ways and may have various forms, and the embodiments are not intended to limit the present invention to the specific disclosed forms, and all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention. It will be understood to include.

In the present specification, when a part "includes" a certain component, it means that it may further include other components, without excluding the other components unless otherwise stated.

Illustrative Of embodiments  Explanation

Hereinafter, exemplary embodiments of the present invention will be described in detail.

Polyamine Hydroxide  Carbon Dioxide Absorbents Including Polymers

In exemplary embodiments of the present invention, it provides a carbon dioxide absorbent comprising a polyhydroxylamine-based polymer represented by the following formula (1) or (2).

[Formula 1]

[Formula 2]

In the formulas (1) and (2), Halide is a halogen element and n is a repeating unit.

Carbon dioxide absorbent comprising a polyhydroxyamine-based polymer according to an embodiment of the present invention is easy to regenerate, as shown in the following [Scheme 1] or [Scheme 2] using water as a solvent when the carbon dioxide absorption / separation described below Since it produces a bicarbonate (bicarbonate, HCO ₃ ) compound there is an advantage that can significantly lower the renewable energy compared to the existing alkanolamine-based absorbent.

Scheme 1

Scheme 2

Therefore, when the carbon dioxide absorbent including the polyamine hydroxide-based polymer according to the embodiment of the present invention is used, carbamate is not formed even after carbon dioxide absorption, so that the absorbent can be regenerated even at a low temperature. In addition to energy savings, corrosion and side reactions resulting from high regeneration temperatures and absorbent loss can be greatly reduced.

In an exemplary embodiment, when measuring the FT-IR spectrum of the polyamine-based polymer represented by Formula 1, -OH peak located in the 3200 to 3600 cm ^-1 region, -CNH located in the 1515 to 1570cm ^-1 region peak, may represent a -CN- positioned -CO- peak, from 1250 to 1360 cm ^-1 region located 900 to 1300 cm ^-1 region.

In an exemplary embodiment, the halogen element may be Cl, I or Br, preferably I.

In an exemplary embodiment, n may be an integer from 1 to 9.

Polyamine Hydroxide  Method for producing carbon dioxide absorbent containing polymer

In exemplary embodiments of the present invention, a method for preparing a carbon dioxide absorbent including a polyhydroxyamine based polymer, comprising: reacting an amine compound, an aldehyde precursor, and an ammonium halide; carbon dioxide comprising a polyhydroxyamine based polymer Provided is a method for preparing an absorbent.

In an exemplary embodiment, the stabilizer and the molecular weight modifier may be further included to react.

In an exemplary embodiment, the reaction may be a condensation reaction, and may be reacted through a method such as stirring at an appropriate temperature and pH. Specifically, at a temperature of 60 to 90 ℃, while maintaining a pH of 2 to 5, it can be reacted by stirring for 1 to 3 hours.

In an exemplary embodiment, the amine compound is urea, melamine, cyanamide, dicyandiamide, guanidine, biguanidine, guanylurea And at least one selected from the group consisting of polycyclic guanidine, and preferably urea.

In an exemplary embodiment, the aldehyde precursor is formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, benzaldehyde, glutaraldehyde, glyoxal, glyoxal, malon It may be at least one selected from the group consisting of dialdehyde (malondialdehyde), succinic aldehyde (succindialdehyde), and phthalaldehyde (phthalaldehyde), preferably glyoxal.

In an exemplary embodiment, the ammonium halide may be at least one selected from the group consisting of NH ₄ Cl, NH ₄ I, and NH ₄ Br, preferably NH ₄ I.

In addition, in order to manufacture a carbon dioxide absorbent including the polyhydroxylamine-based polymer, an amine compound, a stabilizer, and a molecular weight modifier may be added in the manufacturing process. For example, the amine compound may be hydroxyl amine or the like, and may include isopropyl alcohol or the like as the stabilizer and the molecular weight regulator.

CO2 Absorption Method

In exemplary embodiments of the present invention, a method of absorbing carbon dioxide, the method comprising: absorbing carbon dioxide from a gas mixture including carbon dioxide by using an aqueous solution including a carbon dioxide absorbent including the aforementioned polyhydroxyamine-based polymer; It provides a carbon dioxide absorption method.

As described above, the carbon dioxide absorbent including the polyhydroxyamine-based polymer produces a bicarbonate (HCO ₃ ) compound that is easily regenerated by using water as a solvent, thus greatly increasing the renewable energy compared with the conventional alkanolamine-based absorbent. It can be lowered, and compared to other organic solvents, there is an advantage that the handling or price is cheaper.

In an exemplary embodiment, the content of the carbon dioxide absorbent including the polyhydroxylamine-based polymer in the aqueous solution may be 1 to 99 parts by weight, and preferably 3 to 90 parts by weight based on 100 parts by weight of water. When the weight part is less than 1, the carbon dioxide absorption capacity may be lowered, and when the weight part is more than 99 parts by weight, the viscosity may be high and the absorption capacity may be reduced.

CO2 Separation Method

In exemplary embodiments of the present invention, a carbon dioxide separation method comprising: a first step of absorbing carbon dioxide from a gas mixture including carbon dioxide by using an aqueous solution including a carbon dioxide absorbent including the polyamine hydroxide-based polymer described above; And a second step of removing the carbon dioxide absorbed from the aqueous solution including the carbon dioxide absorbent including the polyhydroxyamine-based polymer.

Types of gas mixtures containing carbon dioxide include chemical gases, power plants, steel companies, cement plants, exhaust gases, natural gas, sewage treatment plant biogas, and the like.

In an exemplary embodiment, the content of the carbon dioxide absorbent including the polyhydroxyamine-based polymer in the aqueous solution may be 1 to 99 parts by weight based on 100 parts by weight of water.

In an exemplary embodiment, the absorption temperature of the first step may be 10 to 60 ° C, for example 15 to 50 ° C, preferably 20 to 40 ° C. If the absorption temperature exceeds 60 ℃ desorption proceeds at the same time because the amount of carbon dioxide absorption is reduced, if the absorption temperature is less than 10 ℃ it requires an additional refrigeration equipment to lower the temperature, causing economic problems. .

In an exemplary embodiment, the absorption pressure of the first step may be atmospheric pressure to 50 atmospheres, for example, atmospheric pressure to 40 atmospheres, preferably atmospheric pressure to 30 atmospheres. This is because the pressure of the exhaust gas is atmospheric pressure, so absorption is also most economically achieved. If the absorption pressure exceeds 50 atm, the absorption amount may increase rapidly, but it is necessary to add additional equipment and compressor to increase the pressure. do.

In an exemplary embodiment, the stripping temperature of the second step may be 60 to 120 ° C, for example 65 to 100 ° C, preferably 70 to 90 ° C. If the stripping temperature is less than 60 ℃ because the stripping does not proceed and exceeds 100 ℃ does not have a significant difference from the temperature using the existing absorbent because the advantage of the absorbent according to one embodiment of the present invention is lost.

In an exemplary embodiment, the stripping pressure of the second step may be atmospheric pressure. Removal is difficult to proceed at high pressure, which is required to increase the vapor pressure of the water to maintain this high pressure requires a high temperature, thereby reducing the economics. Therefore, stripping is preferably performed at normal pressure.

In the term used in the specification of the present invention, "atmospheric pressure" means 1 atmosphere as "atmospheric pressure".

Polyamine Hydroxide  Catalyst for regenerating carbon dioxide absorbent containing polymer

Exemplary embodiments of the present invention provide a catalyst for regenerating a carbon dioxide absorbent including a polyhydroxyamine-based polymer represented by Formula 1 or Formula 2 below.

[Formula 1]

[Formula 2]

In the formulas (1) and (2), Halide is a halogen element and n is a repeating unit.

In the case of the catalyst for regenerating a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer material according to an embodiment of the present invention, by having a functional group including a hydroxyl group and an amine group on the surface of the polymer, the carbon dioxide absorbent is efficiently Regeneration (carbon dioxide stripping) is possible, and the energy of the overall absorption process can be saved, as well as the occurrence of corrosion and side reactions and loss of absorbents derived from high regeneration temperatures.

In an exemplary embodiment, when measuring the FT-IR spectrum of the polyamine-based polymer represented by Formula 1, -OH peak located at 3200 to 3600 cm ^-1 region, -CNH located at 1515 to 1570 cm ^-1 region peak, may represent a -CN- positioned -CO- peak, from 1250 to 1360 cm ^-1 region located 900 to 1300 cm ^-1 region.

In an exemplary embodiment, the halogen element may be Cl, I or Br, preferably I.

In an exemplary embodiment, n may be an integer from 1 to 9.

In an exemplary embodiment, the carbon dioxide absorbent is an amine based carbon dioxide absorbent, and the amine based carbon dioxide absorbent may be at least one selected from the group consisting of primary amine, secondary amine, and tertiary amine.

In an exemplary embodiment, the amine-based carbon dioxide absorbent may be at least one selected from the group consisting of monoethanolamine, diethanolamine, and piperazine.

Amine  CO2 Absorbent Regeneration Method

In exemplary embodiments of the present invention, there is provided a method for regenerating an amine-based carbon dioxide absorbent, the method comprising: absorbing carbon dioxide from a gas mixture including carbon dioxide using an aqueous solution including an amine-based carbon dioxide absorbent; And a second step of removing the carbon dioxide absorbed from the aqueous solution containing the amine-based carbon dioxide absorbent using the catalyst for regenerating the carbon dioxide absorbent including the polyhydroxyamine-based polymer described above. to provide.

In an exemplary embodiment, the content of the amine-based carbon dioxide absorbent in the aqueous solution may be 1 to 99 parts by weight based on 100 parts by weight of water.

In an exemplary embodiment, the absorption temperature of the first step may be 10 to 60 ° C, for example 15 to 50 ° C, preferably 20 to 40 ° C. If the absorption temperature exceeds 60 ℃ desorption proceeds at the same time because the amount of carbon dioxide absorption is reduced, if the absorption temperature is less than 10 ℃ because it requires an additional refrigeration equipment for lowering the temperature, causing economic problems. .

In an exemplary embodiment, the absorption pressure of the first step may be atmospheric pressure to 50 atmospheres, for example, atmospheric pressure to 40 atmospheres, preferably atmospheric pressure to 30 atmospheres. This is because the pressure of the exhaust gas is atmospheric pressure, so absorption is also most economically achieved. If the absorption pressure exceeds 50 atm, the absorption amount may increase rapidly, but it is necessary to add additional equipment and compressor to increase the pressure. do.

In an exemplary embodiment, the stripping temperature of the second step may be 60 to 120 ° C, for example 65 to 100 ° C, preferably 70 to 90 ° C. If the stripping temperature is less than 60 ℃ because the stripping does not proceed and exceeds 100 ℃ does not have a significant difference from the temperature using the existing absorbent because the advantage of the absorbent according to one embodiment of the present invention is lost.

In an exemplary embodiment, the stripping pressure of the second step may be atmospheric pressure. Removal is difficult to proceed at high pressure, which is required to increase the vapor pressure of the water to maintain this high pressure requires a high temperature, thereby reducing the economics. Therefore, stripping is preferably performed at normal pressure.

Hereinafter, specific embodiments according to exemplary embodiments of the present invention will be described in more detail. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and the following examples are only common in the art while making the disclosure of the present invention complete. It is to be understood that the invention is intended to facilitate the practice of the invention.

Example  One: Polyamine Hydroxide  Preparation of catalyst for regenerating carbon dioxide absorbent / carbon dioxide absorbent containing polymer

In a three-necked flask equipped with a thermometer, a reflux condenser, and a dropping device, 3.6 g of urea, 2.2 g of ammonium iodide, and 5.2 g of glyoxal were added and stirred at a reaction temperature of 75 ° C. and pH 3 for 2 hours. Thereafter, 0.5 g of hydroxyl amine as an amine compound, 1 g of isopropyl alcohol as a stabilizer and a molecular weight modifier, and 5.2 g of glyoxal were added dropwise over 1 hour through a dropping device to condensation reaction.

The NMR analysis results of the prepared polyhydroxyamine-based polymer were as follows, and used as a carbon dioxide absorbent and a regeneration catalyst, respectively.

1 H-NMR (400 MHz, D2O) δ 4.80 (s, 2H), 4.79-4.29 (m)

13 C-NMR (100 MHz, D 2 O) δ 71.93.

Experimental Example

Experimental Example  One: Polyamine Hydroxide  FT-IR Spectrum Analysis of Polymers

The FT-IR spectrum analysis was performed on the polyamine hydroxide polymer prepared in Example 1. The result is as shown in FIG. 1, -OH peak located in the 3200 to 3600 cm ^-1 region, -CNH peak located in the 1515 to 1570 cm ^-1 region, -CO- peak located in the 900 to 1300 cm ^-1 region, 1250 It can be seen that -CN- located in the region of 1360 cm ^-1 appears.

Experimental Example  2: according to carbon dioxide / nitrogen ratio Polyamine Hydroxide  Of carbon dioxide absorbent containing polymer Absorption

In order to compare the carbon dioxide absorption capacity of the aqueous solution containing 10 parts by weight of the carbon dioxide absorbent prepared in Example 1 with respect to 100 parts by weight of water, the synthesis gas (carbon dioxide / nitrogen 10% / 90%, 30% / 70%) at room temperature, injected into a 100ml aqueous solution at a rate of 30ml / min to measure the total amount and rate of carbon dioxide absorption, it is shown in Figure 2.

Referring to FIG. 2, it can be seen that carbon dioxide mixed with nitrogen in various ratios can be separated.

Experimental Example  3: according to temperature Polyamine Hydroxide  Absorption of carbon dioxide absorbent containing polymer Playback (removal) ability

100 ml of the aqueous solution containing 10 parts by weight of the carbon dioxide absorbent prepared in Example 1 to 10 parts by weight of water, the rate of the synthesis gas (carbon dioxide / nitrogen 10% / 90%) simulating the actual L power plant and steel mill exhaust gas 30 ml / min Injected into a temperature, the total amount and rate of carbon dioxide absorption at atmospheric pressure were measured while changing the temperature to 25 ℃ / 80 ℃, it is shown in FIG.

As can be seen in Figure 3, according to one embodiment of the present invention by using an aqueous solution containing a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer, the carbon dioxide is removed from the carbon dioxide absorbent only by temperature control without other external process conditions (Regeneration), it can be confirmed that the carbon dioxide absorbent can be regenerated. In addition, carbon dioxide can be absorbed / regenerated (removed) even at a temperature (25/80 ° C) that is relatively lower than the absorption / removal condition of a commercially available akanolamine-based carbon dioxide absorber (25/120 ° C). You can check it.

Experimental Example  4: carbon dioxide absorbent regeneration catalyst Refresh rate  Experiment result

Carbon dioxide / nitrogen mixed gas (30/70) was bubbled in a 20% (wt) aqueous solution of monoethanolamine, one of the commercial carbon dioxide absorbents, to regenerate the carbon dioxide absorbent according to Example 1 for a solution in which carbon dioxide was saturated and absorbed. Regeneration was carried out with or without catalyst.

In the regeneration process, the solution temperature was raised to 90 ° C. to measure the amount of carbon dioxide degassed according to the presence or absence of a catalyst. The catalyst used for the repeated experiment was separated by centrifugation and reused repeatedly without drying, and the results are shown in Table 1 below.

Referring to Table 1 below, it can be seen that when the catalyst of Example 1 was used, the regeneration rate was about 2 times better than about 1.5 times.

catalyst	Regeneration temperature (removal temperature) (℃)	Catalyst content compared to absorbent solution (%, wt)	CO2 Regeneration Rate According to Regeneration Time (%)
			10 minutes	20 minutes	30 minutes	60 minutes
No catalyst	90	0	5	29	31	40
Example 1 (polymer catalyst)	90	10	10	40	60	70

Claims (29)

1. Carbon dioxide absorbent comprising a polyhydroxylamine-based polymer represented by the following formula (1) or (2):

   [Formula 1]

   

   [Formula 2]

   

   In the formulas (1) and (2), Halide is a halogen element and n is a repeating unit.
2. The method of claim 1,

   When measuring the FT-IR spectrum of the polyamine hydroxide polymer represented by the formula (1),

   -OH peak located at 3200 to 3600 cm ^-1 region, -CNH peak located at 1515 to 1570 cm ^-1 region, -CO- peak located at 900 to 1300 cm ^-1 region, 1250 to 1360 cm ^-1 region A carbon dioxide absorbent comprising a polyhydroxyamine-based polymer, characterized in that -CN- is located in.
3. The method of claim 1,

   The halogen element is a carbon dioxide absorbent comprising a polyamine hydroxide polymer, characterized in that Cl, I or Br.
4. The method of claim 1,

   N is a carbon dioxide absorbent comprising a polyamine hydroxide polymer, characterized in that an integer of 1 to 9.
5. As a method for producing a carbon dioxide absorbent comprising a polyamine hydroxide polymer according to any one of claims 1 to 4,

   A method of manufacturing a carbon dioxide absorbent comprising a polyamine hydroxide-based polymer, comprising; reacting an amine compound, an aldehyde precursor, and an ammonium halide.
6. The method of claim 5,

   The reaction is a carbon dioxide absorbent production method comprising a polyamine hydroxide polymer, characterized in that the condensation reaction.
7. The method of claim 5,

   The amine compounds include urea, melamine, cyanamide, dicyandiamide, guanidine, biguanidine, guanylurea, and polycyclic guanidine. Method for producing a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer, characterized in that at least one selected from the group consisting of (polycyclic guanidine).
8. The method of claim 5,

   The aldehyde precursor is formaldehyde (formaldehyde), acetaldehyde (acetaldehyde), propionaldehyde (propionaldehyde), butylaldehyde (butylaldehyde), benzaldehyde, glutaraldehyde (glutaraldehyde), glyoxal, malondialdehyde (malondialdehyde) A method of producing a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer, characterized in that at least one selected from the group consisting of succinic aldehyde (succindialdehyde) and phthalaldehyde (phthalaldehyde).
9. The method of claim 5,

   The ammonium halide is a carbon dioxide absorbent manufacturing method comprising a polyhydroxyamine-based polymer, characterized in that at least one selected from the group consisting of NH ₄ Cl, NH ₄ I, and NH ₄ Br.
10. As a carbon dioxide absorption method,

    Absorption of carbon dioxide from a gas mixture containing carbon dioxide by using an aqueous solution containing a carbon dioxide absorbent comprising a polyamine hydroxide polymer according to any one of claims 1 to 4 Way.
11. The method of claim 10,

    The carbon dioxide absorbent containing the polyhydroxylamine-based polymer in the aqueous solution is carbon dioxide absorption method, characterized in that 1 to 99 parts by weight based on 100 parts by weight of water.
12. As a carbon dioxide separation method,

    A first step of absorbing carbon dioxide from a gas mixture comprising carbon dioxide by using an aqueous solution comprising a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer according to any one of claims 1 to 4; And

    And a second step of removing the carbon dioxide absorbed from the aqueous solution including the carbon dioxide absorbent including the polyhydroxyamine-based polymer.
13. The method of claim 12,

    The carbon dioxide absorbent containing the polyhydroxylamine-based polymer in the aqueous solution is carbon dioxide absorption method, characterized in that 1 to 99 parts by weight based on 100 parts by weight of water.
14. The method of claim 12,

    Carbon dioxide separation method, characterized in that the absorption temperature of the first step is 10 to 60 ℃.
15. The method of claim 12,

    The absorption pressure of the first step is carbon dioxide separation method, characterized in that the atmospheric pressure to 50 atm.
16. The method of claim 12,

    The stripping temperature of the second step is 60 to 120 ℃ characterized in that the carbon dioxide separation method.
17. The method of claim 12,

    The stripping pressure of the second step is a carbon dioxide separation method, characterized in that the normal pressure.
18. A catalyst for regenerating a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer represented by Formula 1 or Formula 2 below:

    [Formula 1]

    

    [Formula 2]

    

    In the formulas (1) and (2), Halide is a halogen element and n is a repeating unit.
19. The method of claim 18,

    When measuring the FT-IR spectrum of the polyamine hydroxide polymer represented by the formula (1),

    -OH peak located at 3200 to 3600 cm ^-1 region, -CNH peak located at 1515 to 1570 cm ^-1 region, -CO- peak located at 900 to 1300 cm ^-1 region, 1250 to 1360 cm ^-1 region A catalyst for regenerating a carbon dioxide absorbent comprising a polyamine hydroxide polymer, wherein -CN- is positioned at.
20. The method of claim 18,

    The halogen element is a catalyst for regenerating a carbon dioxide absorbent comprising a polyamine hydroxide polymer, characterized in that Cl, I or Br.
21. The method of claim 18,

    Wherein n is a catalyst for regenerating carbon dioxide absorbent containing a polyamine hydroxide polymer, characterized in that an integer of 1 to 9.
22. The method of claim 18,

    The carbon dioxide absorbent is an amine carbon dioxide absorbent,

    The amine-based carbon dioxide absorbent is one or more selected from the group consisting of primary amines, secondary amines and tertiary amines, carbon dioxide absorbent regeneration catalyst comprising a polyhydroxyamine-based polymer.
23. The method of claim 22,

    The amine-based carbon dioxide absorbent is at least one selected from the group consisting of monoethanolamine (monoethanolamine), diethanolamine (diethanolamine) and piperazine (piperazine), carbon dioxide absorbent for regenerating a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer catalyst.
24. As a method for regenerating an amine carbon dioxide absorbent,

    A first step of absorbing carbon dioxide from a gas mixture comprising carbon dioxide using an aqueous solution comprising an amine-based carbon dioxide absorbent; And

    A second step of removing the carbon dioxide absorbed from the aqueous solution containing the amine-based carbon dioxide absorbent by using a catalyst for regenerating a carbon dioxide absorbent comprising a polyhydroxyamine-based polymer according to any one of claims 18 to 23; A method for regenerating an amine-based carbon dioxide absorbent, comprising.
25. The method of claim 24,

    The content of the amine-based carbon dioxide absorbent in the aqueous solution is 1 to 99 parts by weight based on 100 parts by weight of water, characterized in that the regeneration method of the amine-based carbon dioxide absorbent.
26. The method of claim 24,

    The absorption temperature of the first step is an amine-based carbon dioxide absorbent regeneration method, characterized in that 10 to 60 ℃.
27. The method of claim 24,

    The absorption pressure of the first step is an amine-based carbon dioxide absorbent regeneration method, characterized in that the atmospheric pressure to 50 atm.
28. The method of claim 24,

    The stripping temperature of the second step is an amine-based carbon dioxide absorbent regeneration method, characterized in that 60 to 120 ℃.
29. The method of claim 24,

    The stripping pressure of the second step is an atmospheric pressure regeneration method of the amine-based carbon dioxide absorbent, characterized in that the pressure.

Images