JP2012011333A - Agent for absorbing carbon dioxide, and method of separating carbon dioxide using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agent for absorbing carbon dioxide, for use in stably separating carbon dioxide present in a gas in an energy-saving manner.SOLUTION: The agent for absorbing carbon dioxide comprises a polyalkyleneimine derivative comprising a structure represented by structural formula (I) (in the formula, R, Rand Reach independently represent a hydrogen atom or a 1-3C alkyl group that may contain a substituent, and Rrepresents a hydrogen atom or a 1-2C alkyl group, provided that a substituent constituting R, Rand Ris a hydroxy group, a methoxy group, an ethoxy group, a phenyl group or a methoxycarbonyl group).

Description

  The present invention relates to a carbon dioxide absorbent for absorbing and separating carbon dioxide contained in a gas, and more particularly to a carbon dioxide absorbent for separating stably with energy saving. It is about. The present invention also relates to a method for separating carbon dioxide from a gas containing carbon dioxide such as combustion exhaust gas.

  Conventionally, separation of carbon dioxide contained in a gas has been performed by various methods. For example, carbon dioxide is removed during the ammonia production process, and a method of absorbing and removing carbon dioxide by bringing it into contact with an alkali absorbing solution is generally performed. Such a method is classified as a chemical absorption method, and carbon dioxide chemically absorbed in the absorption tower is released from the absorption liquid and recovered by heating the absorption liquid in the regeneration tower. The chemical absorption process is characterized by high-efficiency carbon dioxide removal and high-purity carbon dioxide recovery. In recent years, carbon dioxide in the atmosphere has attracted attention as a causative agent of global warming, and carbon dioxide in exhaust gas emitted from thermal power plants or steelworks, cement factories, etc., which are large-scale emission sources, is separated and recovered. Consideration has been made. For the separation and recovery of carbon dioxide from such exhaust gas, when the conventional separation and recovery technology represented by the chemical absorption method is used, the specific gravity of the additional energy required for the separation is large, and the economic efficiency is very large. It becomes a problem. In the case of the chemical absorption method, the energy required for this separation is the largest in the process of heating the absorbing solution that has absorbed carbon dioxide and releasing carbon dioxide. As the conventional alkaline solution, an aqueous alkanolamine solution typified by an aqueous potassium carbonate solution or an aqueous monoethanolamine solution is used, and an absorption solution having a smaller separation energy has been studied using these as basic technologies. Patent Document 1, Patent Document 2, Patent Document 3 and Patent Document 4 propose a method for removing carbon dioxide from combustion exhaust gas using a specific low-molecular amine aqueous solution. Patent Document 5 proposes an acidic gas absorbing liquid containing a tertiary alkanolamine and an amine activator. Although these methods are improved over the monoethanolamine aqueous solution, further energy saving and higher efficiency are desired.

  In addition, low-molecular amines such as these absorbing solutions have a problem that a small amount of amine compound evaporates when contacting with exhaust gas in the process of absorbing carbon dioxide. For this reason, reducing the volatility of the amine compound is also considered as one of the problems.

  On the other hand, the use of polymeric amines as carbon dioxide absorbents has also been investigated. Patent Document 6 proposes a carbon dioxide-adsorbing porous resin obtained by addition reaction of a polyvalent amine with porous polymer particles. Patent Document 7 proposes a gas adsorption method using a monodispersed spherical aminomethylated polymer obtained by aminomethylating a polymer of a polyvinyl aromatic compound. However, these techniques do not reduce separation energy, and cannot be applied to large-scale separation such as separation and recovery of carbon dioxide from exhaust gas.

  In the conventional chemical absorption method, the absorbed carbon dioxide is released by thermal energy, and in the process of regenerating the absorption liquid, steam heating is performed to a temperature of about 110 ° C. to 130 ° C., and the absorption liquid is boiled. It is done. For this reason, there is a concern that the amine compound is thermally decomposed in the regeneration process, and the stability of the absorbing liquid in the regeneration process is also considered as one of the problems.

Japanese Patent No. 2871334 Japanese Patent No. 2895325 Japanese Patent No. 3197183 US Patent Application Publication No. 2008-0050296 Japanese Patent No. 2925619 Japanese Examined Patent Publication No. 4-37735 JP 2002-52340 A

  The present invention solves the above-mentioned problems, provides a carbon dioxide absorbent for separating and recovering carbon dioxide contained in gas with energy saving, and further, the amine compound is not volatile and can be used stably. An object is to provide a carbon dioxide absorbent. Another object of the present invention is to provide a method for separating and recovering carbon dioxide from a carbon dioxide-containing gas such as combustion exhaust gas, using the carbon dioxide absorbent.

  That is, the present invention is as follows.

｛式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に水素原子又は置換基を有していてもよい炭素数１〜３のアルキル基であり、Ｒ^４は、水素原子又は炭素数１〜２のアルキル基であり、そしてＲ^１、Ｒ^２及びＲ^３の置換基は、水酸基、メトキシ基、エトキシ基、フェニル基又はメトキシカルボニル基である。｝
で表される構造を含むポリアルキレンイミン誘導体を含む二酸化炭素吸収剤。 [1] The following general structural formula (I):

{Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, and R ⁴ is a hydrogen atom or 1 carbon atom. And a substituent of R ¹ , R ² and R ³ is a hydroxyl group, a methoxy group, an ethoxy group, a phenyl group or a methoxycarbonyl group. }
The carbon dioxide absorber containing the polyalkyleneimine derivative containing the structure represented by these.

  [2] The polyalkyleneimine derivative is obtained by reacting polyethyleneimine with one or more epoxy compounds selected from ethylene oxide, propylene oxide, 1,2-epoxybutane, isobutylene oxide, glycidol and styrene oxide. The carbon dioxide absorbent according to [1].

  [3] The carbon dioxide absorbent according to [1] or [2], wherein a weight average molecular weight Mw of the polyalkyleneimine derivative calculated by GPC of a 0.5M acetic acid aqueous solution is 300 or more and 200,000 or less. .

  [4] The polyalkyleneimine derivative is a hydrophilic-hydrophobic reversible polymer having a hydrophilic-hydrophobic transition temperature in the range of 4.0 ° C. or higher and 96.0 ° C. or lower in the presence of water. ] The carbon dioxide absorbent according to any one of [3] to [3].

  [5] The polyalkyleneimine derivative according to any one of claims 1 to 4 and 10.0% by mass of 10.0% by mass to 90.0% by mass based on the total mass of the carbon dioxide absorbent. The carbon dioxide absorbent according to any one of [1] to [4], which contains 90.0% by mass or less of water.

  [6] A step of absorbing carbon dioxide by bringing the carbon dioxide absorbent according to [5] into contact with a gas containing carbon dioxide, and then heating the absorbent to separate and recover the carbon dioxide. A method for separating and recovering carbon dioxide, comprising:

  [7] The method according to [6], wherein a temperature at which the absorbent is heated is 60.0 ° C. or higher and 100.0 ° C. or lower.

  According to the carbon dioxide absorbent and the carbon dioxide separation and recovery method of the present invention, carbon dioxide can be separated and recovered from gas such as combustion exhaust gas with energy saving. Further, in the present invention, an amine compound that is not volatile and can be used stably can be provided, and a continuous and efficient method for separating and recovering carbon dioxide can be provided.

It is the schematic of the carbon dioxide separation-and-recovery apparatus in the conventional chemical absorption method. It is a schematic diagram of the evaluation apparatus of this invention.

  Hereinafter, embodiments of the present invention will be described in detail. The carbon dioxide absorbent of the present invention is characterized by containing a polyalkyleneimine derivative containing a structure represented by the above general structural formula (I).

[Structure of polyalkyleneimine derivative]
As a result of intensive studies by the present inventors, the polyalkyleneimine derivative contained in the carbon dioxide absorbent of the present invention releases carbon dioxide at a relatively lower temperature than conventional amine compounds after absorbing carbon dioxide. Confirmed to do. Lowering the temperature at the time of releasing carbon dioxide leads to a decrease in thermal energy for raising the temperature of the liquid, and also prevents thermal decomposition of the amine compound and leads to an improvement in stability. As a reason for the improvement of the release ability at low temperature, in the case of a polyalkyleneimine derivative, the thermal property of the polyalkyleneimine derivative chain or the affinity with carbon dioxide or water may be affected. This thermal property or chemical affinity can be controlled by the structure of the epoxy compound. A general polyalkyleneimine has a branched structure. A primary amine is present at the end of the polyalkyleneimine derivative chain, a secondary amine is present in the main chain, and a tertiary amine is present at the branching point. Yes. When this polyalkyleneimine is reacted with an epoxy compound, the primary amine is alkyl-modified to a secondary amine and the secondary amine is alkyl-modified to a tertiary amine. Therefore, a unit having a tertiary amine represented by the general structural formula (I) in the main chain can be introduced according to the reaction amount of the epoxy compound. As for the reaction of amine and carbon dioxide, two equilibrium reactions are known as follows: a reaction for forming a carbamate anion and a reaction for forming a bicarbonate.
<Carbamate anion formation reaction>
2RNH ₂ + CO ₂ → RNHCOO ⁻ · RNH ₃ ⁺
<Bicarbonate production reaction>
RNH ₂ + CO ₂ + H ₂ O → RNH ₃ ⁺ .HCO ₃ ⁻

  Among the above reactions, the carbamate anion formation reaction proceeds with a primary amine and a secondary amine, and the tertiary amine proceeds only with a bicarbonate formation reaction. In general, for many amines, the reaction to generate bicarbonate is known to have a lower heat of reaction than the reaction to generate carbamate anions. Is better. On the other hand, there is a known tendency for the absorption rate to be slow, and the balance between the two reactions is considered important. As a result of intensive studies by the present inventors, it is difficult to control these two reactions by mixing conventional low molecular weight amine compounds, and a plurality of amine structures are provided in the same molecule like polyalkyleneimine derivatives. I found it important.

  In addition, the polyalkyleneimine derivative in the present invention has a hydroxyl group in the side chain. It is speculated that the presence of the hydroxyl group and amino group may cause the above-mentioned thermal properties or chemical affinity to appear remarkably due to the influence of hydrogen bonds between the polymer chains of the polyalkyleneimine derivative or within the same molecular chain. The Further, it was found that the presence of a hydroxyl group makes the polyalkyleneimine derivative highly hydrophilic and particularly excellent in the presence of water. This is because the presence of water molecules is a major factor in the reaction between amine and carbon dioxide, and water molecules are indispensable particularly in reactions that produce bicarbonate. In order to take advantage of such characteristics of the hydroxyl group, it is preferable to select polyethyleneimine as the polyalkyleneimine. This is because the longer the alkyl chain of the polyalkyleneimine, the stronger the hydrophobicity of the main chain, and the smaller the control range of the side chain part associated with the structure selection or reaction amount of the epoxy compound. From the viewpoints of control of hydrophilicity and hydrophobicity and reactivity, the epoxy compound to be reacted with the polyalkyleneimine is particularly preferably ethylene oxide, propylene oxide, 1,2-epoxybutane, isobutylene oxide, glycidol, or styrene oxide.

  Furthermore, the present inventors have found that the hydrophilic-hydrophobic reversible performance of the polyalkyleneimine derivative is utilized in terms of controlling the hydration of the polyalkyleneimine derivative. As used herein, the term “hydrophilic-hydrophobic reversibility” refers to a property or performance in which hydrophilicity and hydrophobicity reversibly change. That is, it was found that the reactivity between amino groups and carbon dioxide can be controlled by the hydrophilic-hydrophobic reversible performance of the polyalkyleneimine derivative. The hydrophilic-hydrophobic reversible performance means that the polyalkyleneimine derivative exhibits a hydrophilic and hydrophobic reversible response due to a change in environmental conditions such as temperature or pH. By using a hydrophilic-hydrophobic transition phenomenon in response to such environmental changes, the reactivity of amino groups and carbon dioxide can be greatly changed to further improve the carbon dioxide absorption / release performance of polyalkyleneimine derivatives. It becomes possible. In applying the hydrophilic-hydrophobic reversible performance of the polyalkyleneimine derivative described above to separation and recovery of carbon dioxide, a polyalkyleneimine derivative whose hydrophilicity and hydrophobicity reversibly changes depending on the temperature environment is excellent. Specifically, a polyalkyleneimine derivative having a hydrophilic-hydrophobic transition temperature at any temperature between 4.0 ° C. and 96.0 in water is preferable. In the present specification, the term “having a hydrophilic-hydrophobic transition temperature” means, for example, a polyalkyleneimine derivative having a transition temperature of 30 ° C., which exhibits hydrophilicity below 30 ° C., and is 30 ° C. or higher. Refers to those that exhibit hydrophobic properties and reversibly transfer these properties depending on the temperature environment. The superiority of this property is that temperature is the most easily controlled factor in the environmental difference between absorption and release, and separation and recovery by the conventional chemical absorption method can also be absorbed under a large temperature difference. This is because the release is repeated. For this large temperature difference (for example, absorption at 40 ° C. and release at 120 ° C.), absorption and release can be repeated with a smaller temperature difference by utilizing the hydrophilic-hydrophobic transition depending on the temperature environment. It becomes possible. When this temperature difference is actually used for the separation and recovery of carbon dioxide and the temperature difference between absorption and release is reduced, the hydrophilic-hydrophobic transition temperature should be 10.0 ° C. or higher and 80.0 ° C. or lower. More preferred. If the transition temperature is too low, the characteristics cannot be used unless the absorption temperature is set low, and if the transition temperature is too high, the characteristics cannot be used unless the release temperature is set high. .

  The present inventors have found that in the above-described polyalkyleneimine derivatives, it is possible to arbitrarily develop and control a hydrophilic / hydrophobic transition phenomenon depending on the structure and reaction amount of the epoxy compound. In addition, the transition temperature of polyalkyleneimine derivatives in water and the transition temperature when carbon dioxide absorbent is used vary depending on the presence of components other than water, and the transition of polyalkyleneimine derivatives in carbon dioxide absorbent depends on these components. It is also possible to adjust the temperature.

  Using the above-mentioned reversible transition phenomenon due to the hydrophilic and hydrophobic temperature environment, when carbon dioxide is absorbed and released continuously and repeatedly, each of the polyalkyleneimine derivatives after absorption and release of carbon dioxide It is necessary to pay attention to the transition temperature. This is because the hydrophilic / hydrophobic transition phenomenon due to heat of the polyalkyleneimine derivative of the present invention depends on the pH, and the alkalinity derived from the amino group becomes weak according to the absorption of carbon dioxide. Therefore, in the case of continuous repeated absorption and release, the properties of the polyalkyleneimine derivative at the time of absorption are affected by the amount of carbon dioxide that remains without being released after release, and at the time of release, the amount of carbon dioxide absorbed after absorption Affected by. First, regarding the polyalkyleneimine derivative at the time of absorption, the carbon dioxide absorption after release is generally 2.0 mol% or more and 30.0 mol% or less with respect to the amino group. In order for the polyalkyleneimine derivative in this state to be hydrophilic at the time of absorption, it should have a transition temperature higher than the temperature at the time of absorption. Specifically, it is desirable that the transition temperature is 15.0 ° C. or higher in a state where any amount of carbon dioxide of 2.0 mol% or more and 30.0 mol% or less is absorbed with respect to the amino group, More preferably, it is 25 ° C. or higher. On the other hand, regarding the polyalkyleneimine derivative at the time of release, the carbon dioxide absorption after absorption is generally 40.0 mol% or more and 90.0 mol% or less with respect to the amino group. The polyalkyleneimine derivative in this state develops a transition between hydrophilicity and hydrophobicity in the process of raising the temperature from the absorption process to the release process, so that it can be hydrophobized at the time of release. Specifically, any of 40.0 ° C. or more and 95.0 ° C. or less in a state in which any amount of carbon dioxide of 40.0 mol% or more and 90.0 mol% or less is absorbed with respect to the amino group. It is desirable to have a transition temperature in the temperature, more preferably 50.0 ° C. or higher and 85.0 ° C. or lower.

[Molecular weight of polyalkyleneimine derivative]
The polyalkyleneimine derivative contained in the carbon dioxide absorbent of the present invention is characterized by utilizing the reactivity of the polyalkyleneimine derivative itself with carbon dioxide. The “polyalkyleneimine derivative” of the present invention is a polymer and has a polymerization degree of a certain level or more. An advantage of using such a polyalkyleneimine derivative as a carbon dioxide absorbing material is that it is not volatile. That is, when carbon dioxide is absorbed by contact with the gas, the amine compound (polyalkyleneimine derivative referred to in the present invention) does not evaporate, so that it is not necessary to remove the absorbent out of the system of the separation and recovery process. As the degree of polymerization, a range generally called an oligomer can be included, and it is desirable to have 10 or more unit units. Accordingly, the molecular weight is not particularly limited, but can generally be selected from a range that is easy to produce. For example, the weight average molecular weight Mw converted from GPC measurement is preferably 500 or more and 200,000 or less, What is necessary is just to select arbitrarily according to the form of a carbon dioxide absorber.

  In addition, what is necessary is just to perform the measurement of the molecular weight by GPC as follows.

A polyalkyleneimine derivative is added to a 0.5 M aqueous acetic acid solution, and a solution which is allowed to stand at room temperature for 24 hours is filtered through a water-resistant membrane filter having a pore diameter of 0.45 μm to obtain a sample solution, which is measured under the following conditions. The sample is adjusted such that the concentration of the polyalkyleneimine derivative is 0.1 to 0.5% by mass.
Equipment: High-speed GPC HLC8220GPC (manufactured by Tosoh Corporation)
Column: Double of Shodex OHpak SB-806M HQ (Showa Denko)
Eluent: 0.5M acetic acid and 0.1M sodium nitrate aqueous solution Flow rate: 1.0ml / min Oven temperature: 40 ° C
Sample injection volume: 0.10 ml

  Moreover, in calculating the molecular weight of the sample, a molecular weight calibration curve prepared using molecular weight standards of standard polyethylene glycol and standard polyethylene oxide (manufactured by GL Science, PEG-10 and PEO-10) is used.

  The amine content in the polyalkyleneimine derivative of the present invention is not particularly limited. However, since it affects the amount of absorbent used per unit carbon dioxide, a larger amount is preferable for energy-saving separation. However, the amine content in the polyalkyleneimine derivative is determined by the structure or reaction amount of the epoxy compound to be reacted. The amine content in the polyalkyleneimine derivative in the present invention is preferably 5.0 mol / kg or more and 15.0 mol / kg or less, more preferably 6.5 mol / kg or more and 12.0 mol / kg or less. It is.

  For the same reason, it is preferable that the content of the polyalkyleneimine derivative in the carbon dioxide absorbent of the present invention is large. However, the content of the polyalkyleneimine derivative is greatly related to the physical properties of the absorbent and must be controlled according to the reactivity with carbon dioxide or the suitability for the process. As a preferable range, it is 10.0 mass% or more and 90.0 mass% or less, More preferably, it is 14.0 mass% or more and 75.0 mass% or less.

  A known method can be used as a method for producing the polyalkyleneimine derivative as described above. Briefly, polyalkyleneimine may be dissolved in water or an organic solvent as necessary, and an epoxy compound may be mixed and heated. The heating temperature has an optimum range depending on the epoxy compound, but is generally in the range of 30 ° C. or more and 100 ° C. or less. In the case of an epoxy compound having a low boiling point such as ethylene oxide, it is preferable to react in an autoclave. Examples of the epoxy compound that can be used in the production of the polyalkyleneimine derivative of the present invention include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, isobutylene oxide, glycidyl methyl ether, and glycidyl ethyl ether. Glycidol, styrene oxide, cyclohexene oxide, glycidyl carboxylate and the like. The reaction amount of the epoxy compound is determined according to the amine content in the polyalkyleneimine, but varies depending on the branching conditions. That is, it is necessary to use more than the terminal primary amine, and conversely, if the number is more than the number of secondary amines, side reactions may occur. In the case of a polyalkyleneimine having a general degree of branching, a reaction at 30 mol% or more and 880 mol% or less is preferable. Two or more of these epoxy compounds can be reacted.

  In addition, the polyalkyleneimine derivative in the present invention can be further reacted with a crosslinking agent having a bifunctional or higher functional group to form a crosslinkable insoluble gel. Examples of such reactive groups include halogenated alkyl groups that are reactive with amino groups, epoxy groups, aldehyde groups, ketone groups, isocyanate groups, acid chloride groups, and the like. Can be made.

  The polyalkyleneimine derivative of the present invention may contain two or more polyalkyleneimine derivatives, and may further contain other components. In the present invention, a material containing a polyalkyleneimine derivative and optionally other constituents is referred to as a “carbon dioxide absorbent”. In particular, it is preferable that the carbon dioxide absorbent contains water that is greatly involved in the reactivity between amines and carbon dioxide. It is preferable to contain 1 equivalent or more of water with respect to the amine content in the carbon dioxide absorbent, but if it is too much, the content of the polyalkyleneimine derivative is relatively reduced, which is not preferable. Specifically, the water content is preferably 10.0% by mass or more and 90.0% by mass or less, more preferably 25.0% by mass or more and 86.0% by mass based on the total mass of the carbon dioxide absorbent. It is below mass%.

  As other components, a solvent may be contained in addition to water as necessary. Depending on the solubility or dispersibility of the polyalkyleneimine derivative, different ones are suitable, but those having a low vapor pressure or boiling point are not preferred because they are volatilized in the separation and recovery step. Also, those having high reactivity with amines are not preferred. From the viewpoint of energy saving, those having low specific heat and good thermal conductivity are preferred. Specific examples of the solvent that may be contained include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, 1,3-butanediol, and 1,4-butanediol, and carbon such as butanol, pentanol, and cyclohexanol. Examples thereof include alcohols having a number of 4 or more, amides such as 2-pyrrolidone, N-methylpyrrolidone, and dimethylacetamide, carbonates such as ethylene carbonate, propylene carbonate, and diethyl carbonate, or silicon oil.

  As other components, a known amine compound may be contained as necessary. It can be contained for the purpose of supplementarily increasing the amount of carbon dioxide absorbed or released. Although there is no restriction | limiting in particular, The thing with a low vapor pressure or boiling point is preferable, and the thing with small heat of reaction with a carbon dioxide is more preferable. Specific examples of amine compounds that can be contained include monoethanolamine, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 1-amino-2-butanol, and aniline. Primary amines such as cyclohexylamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-isopropylaminoethanol, 2-n-butylaminoethanol, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2 Secondary amines such as piperidinoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 3-dimethylamino-1-propanol, 4-dimethylamino-1-butanol, 2-dimethylamino-2-methyl- 1-propanol, N-ethyl-N-methyl ester Noruamin, methyldiethanolamine, ethyl diethanolamine, triethanolamine, N, N-dimethylaniline, tertiary amines such as pyridine, ethylene diamine, diethylene triamine, tetraethylene pentamine, polyethyleneimine, polyvinylamine, polyallylamine, and the like.

  Moreover, you may add well-known polymers other than an above described polyalkyleneimine derivative as another structural component. Further, for the purpose of adjusting the physical properties of the polyalkyleneimine derivative, it is also possible to add an acid, an alkali or a salt. Further, depending on the form of the carbon dioxide absorbent, it is possible to add a known antifoaming agent or dispersion stabilizer, surfactant, viscosity modifier, corrosion inhibitor and the like.

  As a form of the carbon dioxide absorbent of the present invention, it is possible to take various forms such as a dispersion, an emulsion, a powder, and a swollen gel in addition to a solution state. When handled as a powder, fine powdery inorganic particles or resin particles can be added for the purpose of imparting fluidity. Moreover, it is also possible to use it by supporting it on a porous support.

<Separation and recovery method>
The carbon dioxide separation and recovery method of the present invention will be described. The greatest feature of the method for separating and recovering carbon dioxide in the present invention is to use the carbon dioxide absorbent described above. Specifically, carbon dioxide is absorbed by bringing the carbon dioxide absorbent in the present invention into contact with a gas containing carbon dioxide at 10 ° C. to 50 ° C., and then the carbon dioxide absorbent is heated. A method of separating and recovering carbon dioxide is most preferable. In particular, when the carbon dioxide absorbent is handled in a solution state, it can be separated and recovered by the same apparatus and equipment as in the conventional chemical absorption method. An outline of an apparatus in a conventional chemical absorption method is shown in FIG. In FIG. 1, the mixed gas containing carbon dioxide is humidified and cooled as necessary, and then supplied to the absorption tower 11 through the gas supply port 14. The mixed gas pushed into the absorption tower 11 is brought into counter-current contact with the absorbing liquid supplied from the nozzle 12 at the lower filling section 13, carbon dioxide in the mixed gas is absorbed and removed by the absorbing liquid, and the decarbonized gas is in the upper part. It is discharged from the discharge port 19. In the absorption liquid regeneration tower 117, the absorption liquid is regenerated in the lower filling unit 111 by heating by the regeneration heater 110, cooled by the heat exchanger 18 and the cooler 16, and returned to the absorption tower. The carbon dioxide separated from the absorption liquid is cooled by the regeneration tower reflux cooler 116, the water vapor accompanying the carbon dioxide is condensed and separated by the gas-liquid separator 114, and discharged and recovered from the recovered carbon dioxide discharge line 115. .

  Furthermore, when the carbon dioxide absorbent of the present invention is used to separate and recover carbon dioxide, the temperature at which carbon dioxide is released by heating can be lowered. Lowering the temperature at the time of discharge reduces the load on the regenerative heater, reduces the energy required for temperature rise, and enables energy-saving separation and recovery. It is also possible to use unused waste heat by heat exchange or a heat pump. However, since it must be higher than the temperature at the time of absorption, the preferable heating temperature of the carbon dioxide absorbent at the time of release is 60.0 ° C. or higher and 100.0 ° C. or lower. As a still more preferable range, it is 65.0 degreeC or more and 95.0 degreeC or less.

  The gas containing carbon dioxide is not particularly limited, and can be applied to gases having various concentrations, pressures, and temperature conditions. Particularly required for energy saving separation are thermal power plant exhaust gas, steel plant exhaust gas, cement factory exhaust gas, chemical plant exhaust gas, biofermentation gas, natural gas, and the like. Of these gases, those containing an acidic gas other than carbon dioxide as a component are preferably combined with known desulfurization and / or denitration processes.

  Hereinafter, the present invention will be described in detail with reference to examples. In addition, this invention is not restrict | limited by an Example.

<Production example of polyalkyleneimine derivative 1>
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, a polyethyleneimine 20% by mass aqueous solution (SP-200, manufactured by Nippon Shokubai Co., Ltd., amine value 18 mol / g, primary amine: secondary amine: tertiary amine = 35 : 35: 30) 40.0 g was charged and heated to 60 ° C. in an oil bath. Next, 5.0 g of 1,2-epoxybutane and 20.0 g of ethanol were mixed and added dropwise to the reaction vessel over 20 minutes with stirring, and the reaction was allowed to proceed with stirring for 6 hours after completion of the addition. Thereafter, distillation was performed to distill off water and ethanol, followed by drying at 50 ° C. under reduced pressure to obtain polyalkyleneimine derivative 1. From the total organic carbon TOC of the obtained polyalkyleneimine derivative 1 and the C / N value determined from the total nitrogen TN measurement, 47.5 mol% modification was confirmed with respect to 100 mol of the amino group of polyethyleneimine.

<Production example of polyalkyleneimine derivative 2>
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, a polyethyleneimine 20% by mass aqueous solution (SP-200, manufactured by Nippon Shokubai Co., Ltd., amine value 18 mol / g, primary amine: secondary amine: tertiary amine = 35 : 35: 30) 40.0 g was charged and heated to 60 ° C. in an oil bath. Next, 6.5 g of 1,2-epoxybutane and 20.0 g of ethanol were mixed and added dropwise to the reaction vessel over 20 minutes while stirring. After completion of the dropwise addition, the mixture was reacted for 6 hours with stirring. Thereafter, distillation was performed to distill off water and ethanol, followed by drying at 50 ° C. under reduced pressure to obtain a polyalkyleneimine derivative 2. From the total organic carbon TOC and total nitrogen TN measurement of the obtained polyalkyleneimine derivative 2, 62.0 mol% modification was confirmed with respect to 100 mol of amino groups of polyethyleneimine.

  The obtained polyalkyleneimine derivative 1 and polyalkyleneimine derivative 2 were dissolved in water at the composition ratios shown in Table 1, respectively, and an absorbent 1 comprising polyalkyleneimine derivative 1 and water, and polyalkyleneimine derivative 2 And absorbent 2 composed of water and water. Table 1 shows the hydrophilic-hydrophobic transition temperature and aqueous solution concentration of the polyalkylenimine derivative in water, and the amine content (mmol / g) calculated from the total nitrogen TN measurement. Also, absorbents 3 to 5 were prepared as comparative absorbents.

The total organic carbon TOC and total nitrogen TN were measured with the following apparatus.
Total organic carbon: TOC-VCP and TN unit TNM-1 (manufactured by Shimadzu Corporation)
The measurement was performed by dissolving the polyalkyleneimine derivative with water. The modification rate was determined from the difference in C / N before and after the reaction, and the amine content was determined from the value of N.

  The hydrophilic-hydrophobic transition temperature was a temperature at which precipitation of the polyalkyleneimine derivative occurred when the temperature of the aqueous solution or absorbent was increased from 4 ° C. to 96 ° C. at 1 ° C./min. At the same time, the pH was measured, and it was confirmed that the pH started to decrease simultaneously with the precipitation.

Explanation of abbreviations MEA: monoethanolamine EAE: 2-ethylaminoethanol PEI: polyethyleneimine (SP-200 manufactured by Nippon Shokubai Co., Ltd.)

<Method for evaluating carbon dioxide absorbent>
The apparatus shown in FIG. 2 was created. This device circulates gas containing carbon dioxide in a closed system with a pump, absorbs carbon dioxide by ventilating a gas cleaning bottle containing absorbent, and measures the amount of absorption from the concentration of carbon dioxide in the gas. Device. The evaluation method is for the gas supplied from the carbon dioxide cylinder 21 while the valves 25 and 26 are closed and the valve 27 is opened and the pump 211 circulates the gas at a flow rate of 1.5 L / min. The syringe 22 is charged with 500 ml of carbon dioxide, and further adjusted with air so that the carbon dioxide concentration is 17% by volume. A carbon dioxide absorbent is charged into the gas cleaning bottle 214, and the temperature is kept constant by the oil bath 213 so that the internal temperature becomes an arbitrary temperature. Next, the valves 25 and 26 are opened, the valve 27 is closed, the gas containing carbon dioxide is circulated toward the gas washing bottle 214, and the amount of carbon dioxide absorbed by the absorbent is monitored by the carbon dioxide concentration meter 29. To do. After evaluating the absorption performance, the temperature of the oil bath is raised, the absorption amount is measured in the same manner, and the decrease in the absorption amount is evaluated as the release amount. The amount of carbon dioxide absorbed is calculated from the concentration of carbon dioxide and the amount of air 2.85 L calculated from the initial internal volume of the apparatus. The initial volume in the apparatus was calculated from the carbon dioxide concentration by performing the same operation without adding the absorbent. The room was at normal pressure and room temperature.

  Table 2 shows the amount of absorption and release at each absorption agent, absorption temperature and release temperature. The absorption time was 30 minutes, and the release time was 20 minutes after the temperature was raised. Absorption and release are expressed as mole percent of carbon dioxide relative to 100 moles of amine.

  Comparing Examples 1 and 2 with Comparative Examples 1 and 2, it can be seen that the absorbents 1 and 2 of the present invention have a large release amount at 70 ° C., although the absorption amount at 30 ° C. is low. That is, it can be said that the absorbent has a high release performance at a relatively low temperature of 70 ° C. At the same time, the same tendency is shown in Comparative Example 3 using polyethyleneimine not reacted with epoxy, and it can be seen that the change in structure and the content of tertiary amine have a great influence on the release performance. Further, when Examples 2 and 3 are compared, the release amount is greatly increased by changing the release temperature from 70 ° C. to 78 ° C., which is 10% higher than that of Comparative Example 4 performed with a monoethanolamine aqueous solution under the same conditions. It was confirmed that the amount was more than mol%. This result suggests that carbon dioxide can be separated and recovered even in a temperature environment of less than 100 ° C. In addition, it has been confirmed that the polyalkyleneimine derivative used in the present invention is not volatile and is not thermally decomposed at 150 ° C. or lower.

  The present invention can provide a carbon dioxide absorbent for absorbing and separating carbon dioxide contained in gas, and more specifically, carbon dioxide for energy-saving and stable separation. An absorbent can be provided. In addition, a method for separating carbon dioxide from a gas containing carbon dioxide such as combustion exhaust gas can be provided.

DESCRIPTION OF SYMBOLS 11 Absorption tower 12, 112 Nozzle 13, 111 Lower filling part 14 Exhaust gas supply port 15, 17 Absorption liquid circulation pump 16 Cooler 18 Heat exchanger 19 Decarbonized exhaust gas exhaust port 110 Regeneration heater 113 Reflux water pump 114 Gas-liquid separation 115 Recovery carbon dioxide discharge line 116 Regeneration tower reflux cooler 117 Absorption liquid regeneration tower 21 Cylinder 22 Gas syringe 23 Three-way valve 24 Check valve 25, 26, 27 Ball valve 28 Tedlar bag 29 Infrared carbon dioxide concentration meter 210 SUS piping 211 Gas circulation pump 212 Gas flow meter 213 Warm bath 214 Muenke-type gas cleaning bottle (glass, 250 ml)
215 Glass container 216 Condenser

Claims (7)

The following general structural formula (I):

{Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, and R ⁴ is a hydrogen atom or 1 carbon atom. And a substituent of R ¹ , R ² and R ³ is a hydroxyl group, a methoxy group, an ethoxy group, a phenyl group or a methoxycarbonyl group. }
The carbon dioxide absorber containing the polyalkyleneimine derivative containing the structure represented by these.   The polyalkyleneimine derivative is obtained by reacting polyethyleneimine with one or more epoxy compounds selected from ethylene oxide, propylene oxide, 1,2-epoxybutane, isobutylene oxide, glycidol and styrene oxide. 2. The carbon dioxide absorbent according to 1.   The carbon dioxide absorbent according to claim 1 or 2, wherein a weight average molecular weight Mw of the polyalkyleneimine derivative calculated by GPC of a 0.5M acetic acid aqueous solution is 300 or more and 200,000 or less.   The polyalkyleneimine derivative is a hydrophilic-hydrophobic reversible polymer having a hydrophilic-hydrophobic transition temperature in the range of 4.0 ° C. or higher and 96.0 ° C. or lower in the presence of water. The carbon dioxide absorbent according to any one of the above.   The polyalkyleneimine derivative according to any one of claims 1 to 4 and 10.0 mass% or more and 90 mass% or more of 10.0 mass% or less and 90.0 mass% or less based on the total mass of the carbon dioxide absorbent. The carbon dioxide absorbent according to any one of claims 1 to 4, comprising 0% by mass or less of water.   The carbon dioxide absorbent according to claim 5 includes a step of absorbing carbon dioxide by contacting a gas containing carbon dioxide, and then separating and recovering carbon dioxide by heating the absorbent. Carbon dioxide separation and recovery method.   The method of Claim 6 that the temperature which heats the said absorber is 60.0 degreeC or more and 100.0 degrees C or less.

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