WO2014148658A1

WO2014148658A1 - Method for regenerating amine absorbent using proton donor mixture

Info

Publication number: WO2014148658A1
Application number: PCT/KR2013/002328
Authority: WO
Inventors: 백일현; 박기태; 유정균
Original assignee: 한국에너지기술연구원
Priority date: 2013-03-20
Filing date: 2013-03-21
Publication date: 2014-09-25
Also published as: KR20140115089A; KR101485953B1

Abstract

The present invention relates to a method for absorbing and regenerating carbon dioxide by adding and using a proton donor mixture for lowering regeneration energy after an amine absorbent, which is a carbon dioxide absorbent, is absorbed. The method comprises the steps of: preparing a proton donor mixture using an amine and a proton donor precursor; mixing the proton donor mixture with an amine to prepare an absorbent; injecting the absorbent into a carbon dioxide treatment apparatus including an absorption column and a regeneration column, and counter-currently moving the absorbent from the top portion to the bottom portion of the absorption column to absorb carbon dioxide moving from the bottom portion to the top portion of the absorption column; and moving the absorbent passing through the step of absorbing the carbon dioxide to the regeneration column and then regenerating the absorbent. The absorbent in which the proton donor mixture is mixed with the amine exhibits high regeneration efficiency even at a low temperature since the proton donor mixture gives protons to the absorbent when the absorbent is regenerated, and thus can be repeatedly used due to high thermal stability thereof and can have a long use lifespan.

Description

【Specification】

[Name of invention]

Regeneration Method of Amine Absorbers Using Proton Organizer Mixtures

Technical Field

The present application relates to the addition of a proton mixture to lower the renewable energy after the absorption of the amine, a carbon dioxide absorbent, and a carbon dioxide absorption and regeneration method using the same.

Background Art

The technology of separating CO ₂ from exhaust gases is of increasing importance not only for academic and industrial reasons, but also for environmentally beneficial sustainable development. In the situation where coal, petroleum and natural gas are used as the main fuels, the production of C0 ₂ is inevitable. Therefore, the development of cost-effective CO ₂ separation and recovery technology is a key step in reducing CO ₂ .

Carbon dioxide separation and recovery techniques are known as chemical absorption method, physical absorption method or separation membrane separation method, widely applied in natural gas, petroleum, various chemical industries for the purpose of CO ₂ separation, and chemical absorption method is mainly used.

In the case of chemical absorption, it is generally used to remove residual acidic substances. Liquid solutions such as primary, secondary, tertiary, hindered amines, and processed amines are widely used. Hindered amines are often selective in gases containing ： 0 ₂ and S

It is also used to remove H ₂ S.

Currently, the most representative method for absorbing C0 ₂ is chemicals using mixed liquid solutions such as alkanolamines, in particular monoethanolamine (MEA), diethanolamine (DEA), and methyldiethanolamine (MDEA). It is an absorption method. MEA-based technology enables recovery of more than 90% CO ₂ and production of high concentrations of CO ₂ gas above 99%. However, despite these high C0 ₂ separation efficiencies of amine-based technologies, these techniques include constraints on the concentration of amines in solution due to problems such as device corrosion, removal of moisture from recovered gases, loss of absorbents due to volatility, and sulfur content in flue gases. Absorbent deterioration that can occur when regenerating with material or high heat, and absorbent oxidized donor due to bonding with oxygen. Particularly good absorption due to high heat regeneration. I have a disadvantage that requires a lot of energy.

<7> Direct carbamate with carbon dioxide in alkanolamines to reduce high regeneration heat

Sorbents have been developed to reduce carbamate binding ability by attaching methyl or ethyl groups around nitrogen atoms to remove carbon dioxide by carbamate binding, which is typical of AMP (2—amino-2-methyI). -l-propanol). <8> Japanese Patent Application Publication No. 08-103630 discloses an advanced steric hindrance amine technology for a combination of water solution and steric resistance piperazine derivatives, which are absorbents having a large amount of C0 ₂ absorption per mole of absorbent and a unit volume per unit volume, and high absorption rate and low renewable energy. Discloses a technique. However, even in this case, alcohol must be mixed for dissolution of the stereoresist piperazine derivative above a certain concentration, and bicarbonate is formed in the form of a species in which the hindered amine reacts with carbon dioxide. The disadvantage is that reaction is not superior to carbamate-forming reactions.

[Detailed Description of the Invention]

[Technical problem]

The present invention has been made to solve the above-mentioned problems, to provide an amine compound that can remove the carbon dioxide by using a low energy from the carbamate and bicarbonate, a material produced by reacting the amine with carbon dioxide .

Technical Solution

In order to solve the above problem, the carbamate transfers the protons from the two components to the anion component of the carbamate to utilize the principle of separating the amine and carbon dioxide, and bicarbonate also separates carbon dioxide on the same principle. At this time, it was found that the separation efficiency can be improved by adopting an absorbent containing a promoter that gives a proton, thereby completing the present invention.

<π> The present invention comprises the steps of preparing a proton donor mixture using an amine (proton donor precursor); Mixing an amine with the proton donor mixture to prepare an absorbent; Injecting the absorbent into a carbon dioxide treatment apparatus including an absorption tower and a regeneration tower, and moving the countercurrent from the upper end of the absorption tower to the lower end to absorb carbon dioxide moving from the lower end of the absorption tower to the upper end; And regenerating the absorbent having undergone the step of absorbing the carbon oxide in a regeneration tower.

In addition, the present invention, the amine may be a chain amine, benzene amine, poly amine, and piperidine derivative amine (piper idine derivatives) Provided is a regeneration method of an amine absorbent using at least one selected from the group consisting of amines, a proton castor mixture.

<13> The present invention also, the chain amine is 3-isobutoxypropylamine (3-

I sobut oxypr opy 1 am i ne), dimethylaminoethylamine, -2-amino-2-methylpropanol (AMP, 2—Amino-2-methyl ᅳ propanol), nucleomethylenediamine (HMDA, He ame t hy 1 ened i am i ne), Propylamine, Dipropyl amine, Butylamine, Isobutylamine, Hexylamine, 2-Ethyl nucleosilamine (2 -Ethylhexyl amine), Monoethanolamine (MEA), Ethanolamine (DEA, Diethanolamine), Triethanolamine (TEA, Triethanolamine), Methyldiethanolamine (MDEA, Methyldiethanolaraine), Diglycolamine (DGA, Diglycolamine, Allylamine, Methyldial lylamine, Pentylamine, Isoamylamin, N-Methylethylamine, 2-oxylamine (2 Octylamine), 4-aminobutanol, 3-methoxypropylamine (3-

Methoxypropyl amine), and 2-hydroxyxylethylaminopropylamine (2-

Hydroxyethyl aminopropyl amine) provides a method for regenerating an amine absorbent using at least one selected from the group consisting of protons.

<14> The present application, the hexagonal amine is aminopropyl aniline

(Aminopropylaniline), Benzyl amine ᅳ Dimethylbenzylamine

(Dimethylbenzylamine), Dibenzylethanolamine, Tri benzyl amine, Dibenzylamine, N-methylbenzylamine (N-

Methyl benzyl amine), Phenethylamine, 4-benzylpiperidine (4-

Provided is a method for regenerating an amine absorbent using a proton-jujube mixture, which is at least one selected from the group consisting of Benzylpiperidine), Methoxyphenethylamine, and Ethylcyclohexylamine.

<15> The present invention also, the multi-stage amine, polyethyleneimine (PEI, Polyethyleneimine), iminobispropylamine (bis bis-propylamine), methyliminobispropylamine

(Methyl imino_bis 一 propyl amine), Laurilimino bis— propylamine, Pentamethyl diethyl enetri amine, Aminopropyl-1,3-propylenediamine (Aminopropyl-l , 3-propylenediamine), and aminopropyl-1,4-butylenediamine (Aminopropyl-l, 4-butylenediamine), which provides a method for regenerating an amine absorbent using a proton-primer mixture, which is at least one selected from the group consisting of All. <16>

In addition, the present invention, the piperidine derivative amine, n-amino piperidine (n-amino piperidine), n-piperidine ethanol (n—piperidine ethanol), n-methyl-2-piperidine Ethanol (n_methyl 一 2 一 piperidine ethanol), 4 一 piper idine ethanol, η-dimethy-4-piperidone (n-dimethy 卜 4-piper idone), piperazine (Piperazine) ， 2-Methylpiperazine (2-Methylpiperazine), 2,5-dimethylpiperazine (2,5-[) ^ 161; 1 ^ 1] ^ 3 1), 2-Methylpiperazine (2-Methylpiperazine) , ^ Benzyl-4-piperidinola86112 1-4-1) 1 61 (10101), N-methyl -4-piperidone (N-Me thy 1-4 ᅳ pi per i done), N-alkyl-3 -Piperazine (N-Alkyl-3- piperizine), Ν 一 ethylpiperazine (Ν— Ethylpiperazine), pipecolic acid (Pipecol inic acid), methylisonipecotate, N ᅳ alkyl-3-pipepe Choline (N- Alkyl-3-pipecoline), N-Alkylpiper izine, 2-Aminomethylpiperidine, ^ Provides a method for regenerating amine sorbents using protons and mixtures of at least one selected from the group consisting of vagin-4-piperidone 86112 1-4-] ^ 6 ^ (101), and dipiperidinomethan. do.

The present application also includes precursors of the proton-priming complexes, including alkyl sulfonate, alkyl sulfite, imidazol, and pyridin, wherein the alkylsulfonate Alkyl sulfonate is methanesulfonate, ethanesulfonate, propanesulfonate, butansulfonate, pentanesulfonate

pentansulfonate, hexansulfonate, heptanesulfonate

(heptansulfonate), and octansulfonate (octansulfonate) is one selected from the group consisting of, alkyl sulfite (alkyl sulfite) (methansul fite, ethanesul fite, propanesulfite ( group consisting of propansul f ite, butansulfite, pentansulfite, nucleic acid sulfite, sulfonate, heptanesulfite, and octansulfite And imidazole (imi dazo 1) is 1-methyl-3-3-methylimidazole (1 ᅳ me t hy 1-3-me thyl imidazol), 1-ethyl-3-methyl imidazole (1 -ethy i-3-methy 1 imidazol), 1-propyl-3-methylimidazole (1-propy 1-3- methyl imidazol), 1-butyl- 3-methylimidazole (1-butyl— 3- methyl imidazol), 1-nuxyl-3-methylimidazole (1-hexyl-3-methyl imidazol), 1-methyl-2, 3-dimethylimidazole (1-methy 1-2, 3- dimethl imidazol), 1-ethyl-2,3-dimethylimidazole (l-ethyl-2,3-dimethnmidazol), 1-propyl-2,3-dimethylimidazole (1-propy® 2,3-dimethl imidazol), and 1-butyl-2,3-dimethyl Imidazole (l-butyl-2,3 'dimethlimidazol) is selected from the group consisting of, pyridin (pyridin) is n-ethyl- 3' methyl-pyridine (n- ethy '3-methy' pyridin), n- Butyl — 3-methyl-pyridine (n-butyl-3-methyl-pyridin), n—butyl-3–methyl-pyridine (n-butyl_3-methyl-pyridin) n- (3_hydropropyl) -pyridine (n- (3-hydropropyl) -pyridin) n-nuclear sil-4-dimethylamino-pyridine (n-hexy 1-4-diraethylami no-pyr idin), and n-ethyl-3-hydroxymethyl-pyridine (n-ethyl -3-hydroxymethyl-pyridin) provides a method for regenerating amine absorbents using a proton donor mixture.

<19>

The present invention also provides a mixture of protons, including: immersing the amine in a reactor mounted in an ice bath; Excess mixing of the precursor of the proton donor mixture to the sensed amine; And it provides a method for regenerating the amine absorbent using a proton giver mixture, which is prepared through the step of removing the solid material in the reaction water after the mixing step.

<21>

The present application also provides a method for regenerating an amine absorbent using a proton donor mixture, wherein the absorbent mixes 1 to 50 wt% of the proton donor mixture with respect to 100%.

<23>

The present application also provides a method for regenerating an amine absorbent using a proton donor mixture, wherein the absorption degree of the absorption tower is 30 to 60 ^° C.

<25>

The present invention also provides a method for regenerating an amine absorbent using a proton castor mixture, wherein the temperature of the regeneration tower is 90 to 110 ° C.

Advantageous Effects

<27> Absorbents that contain a proton donor mixture in the amine of the present invention show high regeneration efficiency even at low temperature because the proton donor mixture gives a proton during regeneration, and thus can be used repeatedly due to high thermal stability and a long service life. It is effective to have. [Brief Description of Drawings]

Figure 1 shows a mixture of a monoethanolamine absorbent and a monoethanol to give a proton 3:

It is a graph comparing the carbon dioxide regeneration rate according to the temperature of the absorbent mixed with 1.

Figure 2 shows a mixture of a monoethane amine absorbent and a monoethane amine proton 3:

It is a graph of the carbon dioxide concentration according to the regeneration temperature of the absorbent mixed with 1. 3 shows a mixture of protons giving a monoethanolamine absorbent and a monoethanolamine 3:

It is a graph comparing the carbon dioxide regeneration rate according to the temperature of the absorbent mixed in 1.

[Form for implementation of invention]

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily practice the present invention.

Monoethanolamine, classified as primary alkanol amine, reacts with carbon dioxide in aqueous solution to form carbamate (MEA ⁺ C00 ^_ ). The carbamate formed at this time is a very unstable compound and reacts with the surrounding water to quickly convert to carbamate ions (MEAC00—). The total absorption reaction of the monoethanol amine solution and carbon dioxide is as follows.

<33>

<34>

<35> Dissociation of Water:

<36> 2H ₂ 0 ^ H ₃ 0+ + OH ^" (1)

Hydrolysis Reaction of Thicarbonate:

<38> HC0 ₃ + H ₂ 0 C0 ₃ — ² + ¾0 ⁺ (2)

<39>

<40> Deprotonation reaction of alkanolamines:

<4i> MEAH ⁺ + H ₂ 0 ^ MEA + 0 ⁺ (3)

<42> Formation of Bicarbonate:

<43> C0 ₂ + OH ^" HC0 ₃ ^" (4)

<44> HC0 ₃ ^" → C0 ₂ + OH ^" (5)

<45> Carbamate Ion Formation Reaction:

<46> MEA + C0 ₂ + H ₂ 0 → MEAC00— + ¾0 ⁺ (6)

<47> MEAC0 + H30 ⁺ → MEA + C0 ₂ + H ₂ 0 (7)

<48>

The carbamate is a very stable material that is high in order to remove C0 ₂ again. It requires energy. However, removing the protons of the carbamate makes it easier to remove C0 ₂ , thereby reducing the amount of energy required. In one embodiment of the present application, the proton donor mixture is selected as the proton donor of the carbamate, and monoethane is added to the amine solution.

An amine and a proton donor precursor are used to prepare the proton donor mixture. In one embodiment of the present invention, the amine is at least one selected from the group consisting of chain amines, hexagonal amines, benzene amines, poly amines, and piperidine derivatives amines. to be. In addition, the chain amine, 3-isobutoxypropylamine (3-Isobutoxypropylamine), dimethylaminoethylamine (Dimethylaminoethylamine), 2-amino-2-methylpropanol (AMP, 2-Amino-2-methyl-propanol) , Hexamethylenediamine (HMDA), Propyl amine, Dipropylamine ᅳ Butylamine, Isobutylamine, Hexylamine, 2-ethylnuclear amine (2-

Ethylhexylamine, Monoethanolamine (MEA), Ethanolamine (DEA, Diethanolamine), Triethanamine (TEA, Tr iethanolamine), Methyldiethanolamine (MDEA, Methyldiethanolamine), Diglycolamine (DGA, Diglycolamine), allylamine

(Allylamine), Methyldiallylamine, Pentylamine, Isoamylamin, N ᅳ Methylethylamine, 2-Octylamine, 4-Aminobutanol (4-Aminobutanol), 3-methoxypropylamine (3-

Methoxypropylamine), and 2-hydroxylethylaminopropylamine (2-

Hydroxyethylaminopropylamine) is one or more selected from the group consisting of, Hexagonal amine (benzene amine), aminopropylaniline (Aminopropylani 1 ine), benzylamine, dimethylbenzylamine, Dibenzylethanolamine (Dibenzylethanolamine) , Tribenzylamine, Dibenzylamine

Di benzyl amine, N-Methylbenzylamine, phenethylamine

(Phenethyl amine), 4-benzylpiperidine, 4-benzylpiperidine, Methoxyphenethylamine, and one or more selected from the group consisting of Ethyl eye lohexyl amine, The amines are polyethyleneimine (PEI, Polyethyleneimine), Imino-bi s-propylamine, methyliminobis propylamine (Methylimin bis— propylamine), lauryliminobispropylamine

(Lauryl imino-bis-propyl amine), Pentamethyl diethylenetriamine, aminopropyl— 1,3-propylenediamine (Aminopn> pyl-l, 3- propylenedi amine), and at least one selected from the group consisting of aminopropyl-1,4-butylenediamine (Aminopropyl-1,4-butylenediamine), and the piperidine derivative amine is aminopiperidine (n-amino piperidine), n-piper idine ethanol, n-methyl-2-piperidine ethane (n-methyl-2-piper idine ethanol), 4-piperidine ethane (4- iperidine ethano 1) ， n—dimethyl- 4pipiridone (piperazine), piperazine, 2-methylpiperazine, 2,5-dimethylpipe Razine (2,5-Dimethylpiperazine), 2-Methylpiperazine, N-benzyl-4-piperidinol (-Benzy 1-4-piper idinol), N-methyl-4-piperidone (N -Me t hy 1 -4-p iperi done), N_Alkyl-3-piperizine, N-ethylpiperazine (N— Ethylpiperazine), Pipecolinic acid , Methylisonipecotate, N- Alkyl— 3-pipe Choline (N-Alkyl-3-pipecoline;), N-Alkylpiperizine, 2-Aminomethylpiperidine (2-Am i nome thylpiper idine), N_benzyl-4-piperidone (N -Benzy 1-4-piper idone), and dipiperidinomethan is at least one selected from the group consisting of.

In one embodiment of the present invention, the precursor of the proton giver mixture comprises alkyl sulfonate, alkyl sulfite, imidazol, and pyridin. The alkyl sulfonate is methanesulfonate (11 1 ± 311 ^ 1 £ 011 6), ethanesulfonate, propanesulfonate, butansulfonate, butanesulfonate, pentanesulfonate Nate

pentansulfonate, hexansulfonate, heptanesulfonate

(heptansulfonate), and one selected from the group consisting of octansulfonate (octansulfonate), the alkyl sulfite (alkyl sulfite) is methanesulfite (methansulfite, ethanesulfite) propanesulfite (propansulfite) ), Butansulfite, pentansulfite, nucleic acid sulfite, sulfonate, heptanesulfite, and octansulfite One, the imidazole (imi dazo 1) is 1-methyl-3_methylimidazole (l-methyl-3-methy 1 imidazo 1), 1-ethyl-3-methyl imidazole (1 ᅳ et hy 1 -3-met hyl imidazol), 1-propyl-3-methylimidazole (l-pr opy 1-3-methyl imidazol), 1-butyl-3-methylimidazole (1-! 3 ^ 1-3 -11 1; 1 111111 (1 & 201), 1-nucleus-3-methylimidazole (1-hexy 1-3-methyl imidazol), 1-methyl-2, 3-dimethylimidazole (l-methyl- 2 ， 3 ᅳ dimethl i midazol), 1-ethyl-2,3-dimethylimidazole (1-61: 1 1-2，3 ᅳ (111 ^ 111 ^ (13201), 1 ᅳ propyl-2, 3-dimethylimidazole (1 -propy 1-2, 3-dimethl imidazol), and 1-butyl-2, 3-dimethyl Imidazole (l-butyl-2,3-dimethlimidazol) and one selected from the group consisting of the pyridine (pyridin) is n-ethyl-3-methylpypyridine (n-ethyl-3-methyl-pyr idin), n -Butyl-3-methyl-pyridine (n-but y 1 -3— me t hy 1 -pyr idin), n-butyl-3-methyl-pyridine (n-buty 1 -3_methyl-pyridin), n- ( 3-hydropropyl) -pyridine (n- (3-hydropropyl) -pyridin), n-nuclear sil-4-dimethylamino-pyridine (n—hexyl-4—dimethylamir -pyridin), and n-ethyl-3-hydro Oxymethyl-pyridine (n-ethyl-3-hydroxymethy 卜 pyridin).

The amine and the proton donor precursor are reacted in a molar ratio of 1: 1 to prepare a proton donor mixture. In one embodiment of the present application, 1 liter of monoethanolamine as an amine is placed in a reaction vessel mounted in an ice bath, and then cooled, and then 1.2 liters of methanesulfonic acid as a proton donor is slowly introduced into the sensed monoethanolamine. Stir while injecting. At this time, methanesulfonic acid is slightly mixed in excess of monoethanolamine for complete reaction. The reaction is carried out in the ice bath because of the heat generated during the reaction. In order to remove the solid material produced during the synthesis process, a liquid proton mixture is separated using a filter. The proton donor mixture thus prepared becomes a proton donor.

The proton donor mixture is mixed with an amine to prepare an absorbent. In one embodiment of the present invention, the absorbent is mixed with 1 to 50% of the proton donor mixture in comparison to an amine 100 ^ ¾ ''. Generally, amines react with carbon oxides to form carbamate forms ([R ᅳ NH ₃ ] ⁺ [R-NH-C00] ^_ ) and bicarbonate forms ([R-N¾] ⁺ [HC0 ₃ : T) In the desorption process of carbon dioxide absorbed by amines, the proton (hydrogen) of [R-NH ₃ ] ⁺

COO] —) to separate amines and carbon dioxide. Proton and carbamate are 1: 1 in the desorption process, and proton and bicarbamate are 1: 1. In the present invention, the reproducibility may be increased by providing 1 to 50% of the proton donor mixture to the amine, that is, by injecting an excess of protons (H ⁺ ) per 1 mol of carbamate and bicarbamate. This is because the proton compound exhibits an insignificant effect when mixed in a large amount of 50wt% or more because it serves as a promoter.

<54>

Example 55 Absorption and Regeneration of Carbon Dioxide

In order to evaluate carbon dioxide absorption and regeneration, a preliminary experiment of carbon dioxide separation using monoethane amine was performed. Before the experiment, distilled water is injected and heated The internal residue was removed and the temperature inside the process was kept constant. Distilled water used for washing was removed and the prepared solution was placed in a heated state. The solution was withdrawn again and the absorbent solution prepared at the proper concentration was injected through the inlet of the regeneration tower stop. This process is carried out through a valve connected to the regeneration tower. After the injection is completed, the absorbent is heated up by using a heater, and when the absorbent reaches the set temperature, the absorber is operated at a constant flow rate by operating the transfer pump connected to the absorption tower. Was moved into the absorption tower. When the level of the absorbent stored in the lower drum of the absorption tower and the lower drum of the regeneration tower is kept constant, the circulation of the absorbent is started by operating the transfer pump connected to the regeneration tower. When the absorbent is circulated smoothly, carbon dioxide is injected. Carbon dioxide maintained at a constant pressure is preheated by a heater and gas is injected into the lower part of the absorption tower by a gas flow control device. The experiment was carried out by varying the flow rate of gas and liquid by fixing the carbon dioxide flowing into the system at a constant flow rate and adjusting the absorbent flow rate of the transfer pump. Carbon dioxide is moved from the lower end of the absorption tower to the upper end, and at the same time, the absorbent absorbs the carbon dioxide by moving countercurrently from the upper end of the absorption tower to the lower end. The gas from which carbon dioxide has been removed is discharged out of the system through the valve at the top of the absorption tower, and the absorber absorbing carbon dioxide is transferred to the regeneration tower.

Based on the carbon dioxide capture experiment results as described above, a carbon dioxide capture experiment for a proton delivery absorbent was performed. In this experiment, the experimental conditions for the continuous absorption-regeneration capture device are shown in Table 1.

<58> [Table 1]

<59> Laboratory Scale C0 ₂ Absorption Equilibrium Continuous Experimental Conditions

In the exemplary embodiment of the present application, a solution containing 30% by weight of monoethanolamine and 10% of proton conjugates was used as an absorbent in order to capture carbon dioxide by using a proton donor and simultaneously reduce renewable energy. Protons give a mixture of 33% of the mixture, amine monoethane for comparison

A 30 wt% single solution was also used. In this embodiment, after the carbon dioxide absorption and regeneration continuous experiment performed in order to determine the regeneration characteristics, a continuous experiment was performed at a constant temperature of absorption and regeneration. While the experiments were performed continuously, the absorption tower was kept at 60 ^° C and operated while changing the regeneration temperature. Figure 1 shows the difference in the amount of regeneration of the injection C0 ₂ according to the change in the temperature of the heat boiler of the hourly regeneration tower of carbon dioxide regeneration efficiency while increasing the regeneration temperature from 80 ^° C to 1KTC. C0 ₂ removal amount shows the amount to be removed is separated into the upper end portion of the regeneration column C0 ₂ desorption degree of 13.8 vol% C0 ₂ sorbent is injected at the regeneration column. Regeneration of C0 ₂ was not achieved at both regeneration temperatures of 80 ^° C, but the regeneration of co ₂ increased gradually ^at 90 ^° C, 100 ^° C and i05 ° c. Both absorbents reached 100% CO ₂ regeneration. In the 90 ^° C to 105 ^° C section, the CO ₂ removal of the absorbent added with 10 wt¾> protons was higher throughout. In particular, at 90 ^° C, the reproducibility tends to be high, and this phenomenon shows that the proton conjugates play a large role in regeneration.

This phenomenon is understood as the process by which the amine absorbent exchanges protons during the absorption and regeneration process, as shown in the equation below.

That is, the amine reacts with carbon dioxide to produce carbamate ([R-NH ₃ ] [R-NH-C00r), and in the regeneration process for regenerating the separated carbon dioxide, [R- Protons (hydrogen) of NH ₃ ] are given to [R—NH-C00] —) to separate them into amines and carbon dioxide. Therefore, the use of absorbents incorporating such proton-promoting promoters helps to regenerate. On the basis of this principle, the proton donor mixture exhibits higher regeneration efficiency than monoethanolamine even at low temperature because the proton donor mixture gives a proton during regeneration. This seems to be due to the mechanism that separates the protons of the carbamate formed by the C0 ₂ uptake of the proton donor chain proton donor conjugate, which affects the actual regeneration performance.

2 shows the carbon dioxide concentration discharged after absorption in the absorption tower according to the regeneration temperature in the regeneration tower. The figure shows the CO2 concentration in the off-gas from the absorption tower as the regeneration rate in the regeneration tower rises from 90 ^° C to 1 KTC during successive absorption and regeneration processes. At this time, the CO2 concentration of the simulated gas injected is 13.8 vol%, so as the regeneration time passes, the carbon dioxide concentration in the exhaust gas decreases. In the regeneration temperature 110 ° C was confirmed that C0 ₂ is played 100% in both the absorbing solution in a time faster than the refresh rate and C0 ₂ is rapidly increased. For the mono-ethanamine 30wt% fluid absorption in 90 ^° C intervals, while the reproduction of the C0 ₂ that is not at all made 10wt¾> absorbing solution by the addition of common compounds can give a positive character is in the same temperature range showing high reproducibility. It also shows a lot of difference at 100 ^° C.

3 is a view comparing carbon dioxide recovery with temperature in order to look at this phenomenon in more detail. The monoethanolamine absorbent, which contains 10% of the proton compound at 90 ^° C, is more than carbon dioxide. In the same way, monoethane and amine show no carbon dioxide regeneration at all. Regeneration rate decreases as the regeneration silver is raised, but the absorbent mixed with the proton mixture shows high regeneration characteristics.

Therefore, it can be seen that the proton donor chain proton giver improves the regenerative capacity by giving protons when regenerating carbon dioxide and receiving them when absorbed. Such absorbents can reduce capture costs by lowering renewable energy when capturing carbon dioxide.

Claims

[Range of request]

[Claim 1]

Preparing a proton giver mixture using an amine and a proton donor precursor;

Mixing an amine with the proton donor mixture to prepare an absorbent;

Injecting the absorbent into a carbon dioxide treatment apparatus including an absorption tower and a regeneration tower, and moving the counter current from the upper end to the lower end of the absorption tower to absorb carbon dioxide moving from the lower end of the absorption tower to the upper end; And

And moving the absorbent having undergone the step of absorbing carbon dioxide to a regeneration tower, and regenerating it.

Regeneration method of amine absorbent using proton donor mixture.

[Claim 2]

According to that clause 1

The amine is at least one selected from the group consisting of chain amines, benzene amines, poly amines, and piperidine derivatives amines,

Regeneration method of amine absorbent using proton donor mixture.

[Claim 3]

The method of claim 2,

The chain amine is 3-isobutoxypropylamine (3-Isobutoxypropylamine), dimethylaminoethylamine (Dimethylaminoethylamine), 2-amino- 2-methylpropanol (AMP, 2-Amino-2-methyl-propanol), nucleus yarn Methylenediamine (HMDA, Hexamethylenedi amine), Propylamine, Dipropylamine, Butylamine, Isobutylamine, Hexylamine, 2-ethylnuclear amine (2-

Ethylhexyl amine), Monoethanolamine (MEA, Monoethanol mine), Ethanolamine (DEA, Diethanolamine), Triethaneamine (TEA, Triethanolamine), Methyldiethanolamine (MDEA, Methyldiethanolamine), Diglycolamine (DGA , Diglycolamine), Allylamine

(Allylamine), Methyldial lylamine, Pentylamine, Isoamylamin, N-Methylethylamine, 2-Octylamine, 4-Amino Butanol (4-Aminobutanol), 3-Methoxypropylamine (3-

Methoxypropylamine), and 2—hydroxylethylaminopropylamine (2-

At least one selected from the group consisting of Hydroxyethylaminopropylamine, Regeneration method of amine absorbent using proton donor mixture.

[Claim 4]

The method of claim 2,

The hexagonal amines include aminopropylaniline, benzylamine and dimethylbenzylamine.

(Dimethyl benzyl amine), di-benzyl ethanolamine ^{(Dibenzylethanolamine;),} tree benzylamine (Tribenzylamine), dibenzylamine (Dibenzylamine), N- methyl-benzyl amine (N-

Methyl benzyl amine), Phenethylamine, 4-benzylpiperidine (4-

At least one selected from the group consisting of Benzylpiper idine, Methoxyphenethylamine, and Ethylcyclohexylamine

Regeneration method of amine absorbent using proton donor mixture.

[Claim 5]

The method of claim 2,

The multi-stage amine is, polyethylenimine (PEI, Polyethyleneimine), Imino-bi s-propyl amine (Methyl imino- b is one propyl amine), Lauryl imino no bis-propyl amine, pentamethyl diethylenetriamine, aminopropyl-1,3-propylenediamine (Aminopropyl-l, 3- propylenediamine) and regeneration method of an amine absorbent using protons, which is at least one selected from the group consisting of aminopropyl-1,4-butylenediamine.

[Claim 6]

The method of claim 2,

The piperidine derivative amine is n-amino piperidine, n-piper idine ethanol, n-methyl-2-piperidine ethanol (n-methyl- 2-piperidine ethanol), 4-piperidine ethane (4-piper idine ethanol), n-dimethyl-4-piperidone (n-dimethyl-4-piperidone), piperazine (Piperazine;), 2-methyl Piperazine (2-Methylpiperazine), 2,5-dimethylpiperazine (2,5-1) ^^ 1: 1 1 ^ ^ 3 1), 2-Methylpiperazine, N-benzyl-4 -Piperidinol (N— Benzyl-4-piper idinol), N ᅳ methyl-4-piperidone (N-Me t hy 1-4-p iperi done), N-alkyl-3-piperazin (NA 1 ky 1 -3-p iperizine, N—N-Ethylpiperazine, Pipecolinic acid, Methyl isonipecotate, N-alkyl-3-pipecoline (N-Alkyl -3-pipecoline), N-Alkylpiperizine, 2-aminomethylpiperidine (2- At least one selected from the group consisting of aminomethylpiperidine, benzyl-4 ᅳ piperidone (^ 86112 1-4-1 ^ 1 (101), and Dipiperidinomethan,

Regeneration method of amine absorbent using proton donor mixture.

[Claim 71

The method of claim 1,

The precursors of the proton conjugates include alkyl sulfonate, alkyl sulfite, imidazol, and pyridin, the alkyl sulfonate being methanesulfonate methansulfonate, ethanesulfonate, propanesulfonate (1 31 ^ 1 £ 01 ^^, butansulfonate, pentansulfonate, nucleic acidsulfonate

hexansulfonate, heptanesulfonate, and octansulfonate, wherein the alkyl sulfite is methanesulfite, ethanesulfite, Propansulfite, butansulfite, pent ansulfite, hexansulfite, sulfonate, heptanesulfite, and octanesulphite octansulf ite), and the imidazol is 1-methyl-3-methyl imidazol or 1-ethyl ᅳ 3-methylimidazole. (1-ethyl ᅳ 3-methyl imidazol), 1-propyl-3-methylimidazole (1-propyl-3-methyl imidazol), 1-butyl- 3-methylimidazole (1-buty 卜 3-methyl imidazol), 1-nuxyl-3-methylimidazole (l-hexyl-3-methylimidazol), 1-methyl-2,3-dimethylimida (1-methy 1-2, 3-dimethl imidazol), 1-ethyl-2, 3-dimethylimidazole (1-ethyl-2, 3-dimethl imidazo 1), 1-propyl-2, 3 ᅳ dimethyl Midazole (1-propy 1-2, 3-dimethl imidazol), and 1-butyl-2,3-dimethylimidazole (l-butyl-2,3—dimethlimidazol), the pyridine (pyridin) is n-ethyl-3-methyl-pyridin, n-butyl-3-methyl-pyridin, n-butyl-S-methyl-pyridin 3-methyl-pyridine, n- (3-hydropropyl) pypyridine, n- (3-hydropropyl) -pyridin, n-nuclear 4-dimethylamino- Pyridine (n-hexy 卜 4-dimethylamino-pyridin), and 11-ethyl-3-hydroxymethyl-pyridine (11-61: 1 1-3 ᅳ hydroxymethyl-pyridin),

Regeneration Method of Amine Absorbers Using Proton Organizer Mixtures

[Claim 8]

The method of claim 1, The proton give compound is,

Cooling the amine by putting it in a reaction vessel mounted in an ice bath;

Excessively mixing a precursor of the proton-juvenant mixture to the cooled amine; And

It is prepared through the step of removing the solid material from the semi-aungung passed through the mixing step,

Regeneration Method of Amine Absorbers Using Proton Organizer Mixtures.

[Claim 9]

The method of claim 1,

The absorbent is amine 100wt? to mix 1 to 50% of the proton donor complex in contrast to

Regeneration method of amine absorbent using proton donor mixture.

[Claim 10]

The method of claim 1,

The temperature of the absorption tower is 30 to 60 ^° C

Regeneration method of amine absorbent using proton donor mixture.

[Claim 11]

The method of claim 1,

Silver of the regeneration tower is 90 to 110 ^° C,

Regeneration method of amine absorbent using proton donor mixture.