WO2014118633A2

WO2014118633A2 - Carbon capture solvents and methods for using such solvents

Info

Publication number: WO2014118633A2
Application number: PCT/IB2014/000419
Authority: WO
Inventors: Prateek Bumb; Ramesh Kumar AUSULA; Aniruddha SHARMA
Original assignee: Carbon Clean Solutions Pvt Ltd
Current assignee: Carbon Clean Solutions Pvt Ltd
Priority date: 2013-01-31
Filing date: 2014-01-31
Publication date: 2014-08-07
Anticipated expiration: 2015-07-31
Also published as: EP4427835A1; EP2950910A4; FI2950910T3; EP2950910A2; WO2014118633A3; US10239014B2; ES3014995T3; EP2950910B1; DK2950910T3; US20160193563A1

Abstract

A solvent for recovery of carbon dioxide from gaseous mixture, having alkanolamine, reactive amines acting as promoter or activators, glycol, and a carbonate buffer. A solvent for recovery of carbon dioxide from gaseous mixture, having alkanolamine, reactive amines acting as promoter or activators, sulfolane, and a carbonate buffer. One specific solvent contains less than about 75% by weight of water and has a single liquid phase.

Description

CARBON CAPTURE SOLVENTS AND METHODS FOR USING SUCH SOLVENTS

STATEMENT OF RELATED APPLICATIONS

This patent application claims the benefit of U.S. provisional patent application No. 61/759,191 having a filing date of January 31, 2013, which is incorporated herein in its entirety by this reference.

BACKGROUND

This disclosure relates to a method for the preparation of solvents and methods for treatment of industrial effluent gases, and, more specifically, this disclosure relates to solvents and process for using these solvents to aid in the removal of carbon dioxide (C0₂) from other sources such as power plants or industrial utility.

SUMMARY

This disclosure is directed towards a solvent for recovery of carbon dioxide from gaseous mixture having an alkanolamine, reactive amines acting as promoter or activators, and a carbonate buffer. One specific solvent contains less than about 75% by weight of dissolving medium water and glycol (e.g., polyethylene glycol) and has a single liquid phase. Another specific solvent contains less than about 75% by weight of dissolving medium water and glycol (e.g., polyethylene glycol) and has a single liquid phase. Another specific solvent contains less than about 75 %> by weight of dissolving medium water and sulfolane and has a single liquid phase.

Additional features of the disclosure will become apparent to those skilled in the art upon consideration of the following detailed description of illustrative embodiments exemplifying the best mode of carrying out the disclosure as presently perceived.

BRIEF DESCRIPTION OF THE DRAWINGS

The detailed description particularly refers to the accompanying figures in which:

FIG. 1 is a schematic picture of the reaction; and

FIG. 2 is a perspective view of one illustrative embodiment. FIG. 3 shows a viscosity plot of one exemplary solvent. DEFINITIONS

As used herein, the term "solvent" can refer to a single solvent or a mixture of solvents. DETAILED DESCRIPTION

This disclosure includes several aspects and provides methods and solvents that, when used alone or in combination, may significantly reduce or eliminate carbon dioxide (C0₂) emissions from industrial plants that burn solid fuels, particularly coal-fired power plants. This disclosure is directed to C0₂ capture/sequestration from flue gases C0₂ emissions should also be applicable to C0₂ capture from gas and oil fired boilers, combined cycle power plants, coal gasification, and hydrogen plants, biogas plants.

As shown in FIG. 1, the vapor and liquid phases are contact in a small cross-section. In treating the emissions, the absorption step involves removal of acid gases and other components from the gas phase by transport into the liquid phase. The gas-liquid interface separates the phases. An absorbing gas dissolves into the liquid at the interface, then diffuses across a thin layer of liquid (termed the diffusion layer) of one specific solvent. As it diffuses, the gas meets the reactive absorbent component in one specific solvent, reacts with it, and generates heat and reaction products such as carbonate. Reaction products can diffuse into the bulk liquid while the liberated heat of reaction heats the liquid. In one example, there is a mixture of tertiary amine/hindered amine, reactive amines (e.g, a polyamine activator), carbonate buffer, a dissolving medium of water and physical polyethylene glycol as to solvent system remain as a single liquid phase in removing acidic gases from gaseous mixture.

In embodiment, one specific solvent for absorbing C0₂ includes alkanolamines, which can be any one of compounds represented by following formulae (I) to (III) or a mixture thereof:

H:rogif H-'i;o sitaiis sig compound (!)

Ni rogeis-coBti amg eof& ouad (II)

com o nd (iil)

in the formulae (I) to (III): x and y respectively satisfy relationship: 1 less than or equal to 5 and 2. less than or equal to 10; and R¹, R², R³, and R⁴ represent— QH_jO_kNi (where i=0 to 10, j=l to 21, k=0 to 5, and 1=0 to 5).

In one illustrative solvent, reactive amines can be any one of nitrogen containing compounds represented by following formulae (IV) to (XIII) or mixture thereof. Reactive amines may be nitrogen-containing compound having a secondary nitrogen in a ring or a nitrogen-containing compound having a tertiary nitrogen in a ring.

In another illustrative solvent, reactive amines can be a nitrogen-containing compound having secondary and tertiary nitrogen in a ring.

In another illustrative solvent, reactive amines can be a nitrogen-containing compound having a nitrogen in a substituent group branching from the ring.

In another illustrative solvent, reactive amines can be nitrogen-containing compound may be a nitrogen-containing compound having a primary nitrogen in a substituent group branching from the ring.

In another illustrative solvent, reactive amines can be a nitrogen-containing compound having three nitrogen atoms or more in a molecule thereof.

In another illustrative solvent, reactive amines can be a nitrogen-containing compound having in a molecule thereof all of primary, secondary, and tertiary nitrogens. — x — — ¾:— κ— ;r

in the formulae (IV) to (V): R⁵ and R⁶ represent -- CiH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R⁷ and R⁸ represent -- CiH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

in the formula (VI): R⁹ and R¹¹ represent - CiH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R10 represents - CiH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

in the formula (VII): R⁹ and R¹¹ represent -CiH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R¹⁰ and R¹² represent -CiH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

Nsfc'o tin- o uiiS ig compound (VIII)

in the formula (VIII): R⁹ represents ~ QH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R¹³, R¹⁴, R¹⁵ and R¹⁶ represent -- CiH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

Nitro cK-conSasniKg com omsd (DC) in the formula (IX): R9 and R18 represent -CiH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R10, R15 and R17 represent -QH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

m the formula (X): R⁹ represents -QH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R¹³, R¹⁴, R¹⁶ and R¹⁹ represent -CiH_jO_k i (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

in the formula (XI): R⁹ and R¹⁸ represent -CiH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to

5, and 1= =00 ttoo 5); and R¹⁴, R¹⁷ and R²⁰ represent --CiH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5 and 1=0 to 5),

in the formula (XII): R⁹ and R²¹ represent -CiH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R¹⁴, R¹⁶ and R¹⁷ represent -CiH_jO_k i (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

·^*.·.:· : .■· ··:· :·. e«a¾jw¾iw

in the formula (XIII): R⁹ and R¹⁸ represent -CiH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R¹⁴, R¹⁶ and R¹⁷ represent -CiH_jO_k i (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5).

In one specific solvent, the second compound component may be any one of nitrogen- containing compounds represented by following formulae (XIV) to (XIX) or a mixture thereof:

in the formula (XIV): R²² represents -CiH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R²³ and R²⁴ represent -CiH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

^{■ '}i -ogfeR- iJstaasijsg eosnposiad (XV) in the formula (XV): R²⁵ represents - H_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R23 and R²⁶ represent -CiH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to

in the formula (XVI): R²³, R²⁷ and R²⁸ represent --CiH_jO_kN_! (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

:^ί- ί:··ί:··:!ϊ:¾:-:^·χ ..·:"¾¾ν·::;_::·; -NY:.: : in the formula (XVII): R²² represents -OToW (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R²³, R²⁴, R²⁷ and R²⁹ represent -CiH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

^ -*>1S , xrrr i 2<i itmgea-co t ii iig compound. ( VIII.) in the formula (XVIII): R²⁵ represents -QH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5); and R²³, R²⁶ and R²⁹ represent -QH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5),

in the formula (XIX): R , R , R and R^2y represent --CiH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5)

In one specific solvent, the reactive amine may be a nitrogen-containing compound represented by following formula (XX):

in the formula (XX): R , R , R^jj and R^J4 represent -QH_jO_kNi (where i=l to 10, j=0 to 26, k=0 to 5, and 1=0 to 5), and R³¹ represents -QH_jO_kNi (where i=0 to 10, j=0 to 26, k=0 to 5, and 1=0 to 5).

In one specific solvent, the reactive amine may be piperazine, N-2-Hydroethyl

Piperazine, 2-aminomethyl piperazine or mixture thereof.

Piperazine

N-2-Hydroethyl Piperazine

2-aminomethyl piperazine

In one illustative solvent, one of one specific solvent components can be represented by polyethylene glycol (PEG) represented by the following formulae (XXI) and / or physical pressure driven solvent or mixture thereof:

Polyethylene Glycol (C2_nH4_n+20_n+i)

H-(0-CH₂-CH₂)_n-OH

where, n=integer

Glycols suitable with specific embodiments include monoethylene glycol (EG), Diethylene Glycol (DEG), Triethylene Glycol, Tetraethylene Glycol, Methoxytriglycol (MTG). Other physical solvent used as a solvent component are Sulfolane, N-Methyl-2-Pyrrolidone (NMP).

In one specific solvent, alkanolamines may be contained in an amount in a range from equal to or larger than 10 wt % to equal to or less than 40 wt %, reactive amines may in an amount in a range from equal to or larger than 6 wt % to equal to or less than 40 wt %, and a total amount of the alkanolamine and reactive amines may be more than 20 wt % to equal to or less than 80 wt %.

In one specific solvent, the alkanolamine may be represented by the formula (I), where

1 2

each of R and R is H.

In one specific solvent, the alkanolamine may be represented by the formula (I), where x is 2 to 4 and y is 4 to 8.

In one specific solvent, alkanolamines may be represented by the formula (I), where R¹ is H and R is -CmHnOoNp (where m=l to 5, n=l to 11, o=0 to 5, and p=0 to 5).

In one specific solvent, the alkanolamine may be represented by the formula (I), where x is 2 to 4, y is 4 to 8, and R² is CH₃, C₂H₅, C₃H₇, or C₄¾.

In one specific solvent, the alkanolamine may be represented by the formula (I), where Rl and R represent -CmHnOoNp (where m=l to 5, n=l to 11, o=0 to 5, and p=0 to 5).

In one specific solvent, the alkanoamine may be represented by the formula (I), where x is 2, y is 4, R¹ is CH₃, and R² is C₂H₄OH. An absorbent liquid for absorbing C0₂ or H₂S or both from gas according to certain embodiments includes a cyclic amine compound having one nitrogen in a ring. In one specific solvent, the cyclic amine having one nitrogen in a ring may be a cyclic amine having one nitrogen in a 5-membered ring, 6-membered ring, or 7-membered ring.

In one specific solvent, the cyclic amine having one nitrogen in a 5-membered ring, 6- membered ring, or 7-membered ring may be pyrrolidine (PR), piperidine (PZ), or hexamethyleneimine (HMI).

In one specific solvent, the cyclic amine compound having one nitrogen in a ring may be a nitrogen containing compound having a primary nitrogen in a substituent group branching from the ring.

In one specific solvent, the nitrogen-containing compound having a primary nitrogen in a substituent group branching from the ring may be aminomethylpiperidine or aminoethylpiperidine.

In one specific solvent, the cyclic amine compound having one nitrogen in a ring may be a nitrogen-containing compound having a hydroxyl group in a 5-membered ring, 6-membered ring, or 7-membered ring.

In one specific solvent, the nitrogen-containing compound having a hydroxyl group in a 5-membered ring, 6-membered ring, or 7-membered ring may be piperidinol (PDN).

An absorbent liquid includes a mixture of one specific solvent, and an alkanolamine. In one specific solvent, the alkanolamine may be monoethanolamine (MEA), ethylaminoethanol (EAE), triethanolamine, N-methyldiethanolamine (MDEA), diisopropanolamine, diglycolamine, or a mixture thereof.

An process for removing C0₂ or H₂S or both a includes an absorption tower that allows gas containing C0₂ or H₂S or both and an absorbent liquid to be in contact with each other to remove C0₂ or H₂S or both from the gas; and a regeneration tower that regenerates a solution which has absorbed the C0₂ or H₂S or both, the absorption tower reusing the solution regenerated at the regeneration tower by removing the C0₂ or H₂S or both from the solution.

In one embodiment, one specific solvent for recovery of carbon dioxide from gaseous mixture includes hindered amine, reactive amine, Polyethylene glycol, and a alkali carbonate buffer. The remaining solvent may be water. Reactive amines may be a piperazine and its derivative such as piperazine, 2- aminomethyl piperazine, aminoethylpiperazine, hydroxyethylpiperazine, 3-(3- pyrrolidyl)piperidine, 2-(3-pyrrolidyl)piperazine, 3-(3-piperidyl)-piperidine, 3-(2- piperazinyl)piperidine, or 2-(2-piperazinyl)piperazine, 2-aminomethyl piperazine. The reactive amine may be ethylenediamine, dimethyl ethylenediamine, pyrazolidine, imidazolidine, 2-(2- pyrrolidyl)-pyrrolidine, 2-(2-imidazolidyl) imidazolidine or mixture thereof. One example includes a solvent having hindered amine, mixture of active amine piperazine and N-2 Hydroethyl Piperazine, a carbonate buffer, polyethylene glycol, and water.

One embodiment may include a solvent with poly ethylene glycol, any of a class of organic compounds belonging to the alcohol family; in the molecule of a glycol, two hydroxyl (OH) groups are attached to different carbon atoms. The term is often applied to the simplest member of the class, ethylene glycol. Ethylene glycol, also called 1 ,2-ethanediol, molecular formula HOCH₂CH₂OH, is a colourless, oily liquid possessing a sweet taste and mild odor. It can be produced commercially from ethylene oxide, which is obtained from ethylene. Further, propylene glycol, also called 1,2-propanediol, resembles ethylene glycol in its physical properties. Other glycols include 1,3-butanediol, 1,4-butanediol, 2-ethyl-l ,3-hexanediol, and 2- methyl-2 -propyl- 1,3 -propanediol, methoxytri glycol and others and are suitable herewith.

One specific solvent may contain hindered or tertiary amines that act as high C0₂ loading carrier as the base solvent to increase the capacity of the CO₂ capture solvent. Hindered amine / tertiary amine may be N-methyldiethanolamine (MDEA), 2-(2-aminoethoxy)ethanol, Aminoethylethanolamine (AEEA), 2-amino-2methyl-l-proponal (AMP), 2-(ethyamino)-ethanol (EAE), 2-(methylamino)-ethanol (MAE), 2-(diethylamino)-ethanol (DEAE), , diisopropanolamine (DIPA), methylaminopropylamine (MAPA), 3-aminopropanol (AP), 2,2- dimethyl- 1,3 -prop anediamine (DMPDA), 3-amino-l-cyclohexylaminopropane (ACHP), diglycolamine (DGA), l-amino-2-propanol (MIPA), 2-methyl-methanolamine (MMEA); Di ethyl ethanol amine (DEEA)

One specific solvent may contain a carbonate buffer. The pH may range for a carbonate buffer may be between 8.0 and 9.0. Carbonate in one specific solvent increases the pH of one specific solvent. This high pH allows for increased carbon dioxide capture in the form of bicarbonate salts. The carbonate can be regenerated when one specific solvent is heated. In some instances percarbonate may contribute to the buffer system.

Suitable carbonate buffer salts are described herein. The amount of carbonate buffer salt used in the buffer system is an amount that is sufficient, when used with the remaining components, to raise salivary pH to a pH of about 7.8 or more, about 8.5 or more, and about 9 or more (e.g., about 9-11), irrespective of the starting pH.

In another embodiment, the carbonate salt is selected from the group consisting of sodium carbonate, potassium carbonate, calcium carbonate, ammonium carbonate, and magnesium carbonate. In yet another embodiment, the bicarbonate salt is selected from the group consisting of sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, ammonium bicarbonate, and magnesium bicarbonate. In one embodiment, the binary buffer system comprises sodium carbonate and sodium bicarbonate. In another embodiment, the sodium bicarbonate is dessicant-coated sodium bicarbonate.

The amount of carbonate buffer and reactive amine piperazine in the solution is limited by the solubility of both components in water, thus resulting in solid solubility limit for aqueous solutions. At 25 C, the solubility of potassium carbonate buffer in a C0₂ rich solution is 3.6 m and the solubility of piperazine in water is approximately 2 m. With the solid solubility limitation, the resulting lower concentration can result in slow reaction rate and low solution capacity. By combining piperazine and carbonate buffer solubility in polyethylene glycol and aqueous solutions, the resultant solubility increases.

Reactive amines such as piperazine and C0₂ react, it undergoes equilibrium reaction to form piperazine carbamate and piperazine dicarbamate and some free and bound piperazine. Because of the addition of carbonate buffer salt; which react with free and bound piperazine in reacting more C0₂ to form piperazine carbamate and piperazine dicarbamate.

The ratio of equivalents of carbonate salt to equivalents of reactive amine can be between 0.3 - 3.0. The concentrations of the reactiveamine and carbonate salt can be between 3.0 - 8.0 equivalents/Kg H₂0 or 4.0 and 6.0 equivalents/Kg H₂0. The amount of piperazine and carbonate buffer salt can be adjusted based on the solubility in water and polyethylene glycol.

In one example, one specific solvent and method of use for the removal of C0₂ from flue gas, natural gas, hydrogen gas, synthesis gas, and other process and waste gas streams. One specific solvent may contain a carbonate buffer, a reactive amine, a hindered amine, and a polyethylene glycol, resulting in the solution pH between (10 - 13.5) in absence of C0₂. The reactive amine 6 wt% to 40 wt% with the total concentration limited by the solid solubility of the reactive amine in aqueous and polyethylene glycol solution or of the carbonate buffer salt from 0.15 wt% - 10 wt% with total concentration limited by the solid solubility in aqueous solution. This chemical solvent is designed to increase the rate of C0₂ removal to improve the efficiency of a removal process.

Piperazine is freely soluble in water and solubility in ethylene glycol up to a about 20 wt%. Carbonate buffer salt solubility in water is 112 g/100 mL at 20 °C,

The temperature of the solution when contacting with the gaseous stream may be between approximately30 C - 125 C. The rate constant for the reaction of C0₂ with the

3 3

piperazine derivative (K_PZ) may be at least 25 m /mol-s at 25 C, or at least 50 m /mol-s at 25 C.

In one embodiment, one specific solvent has a reactive amine in concentration between about 6 wt% and 40 wt%.

In yet another embodiment, one specific solvent has a alkanolamine in a concentration between about 10wt% and 40 wt%.

In yet another embodiment, one specific solvent has a carbonate buffer has concentration between about 0.15wt% - 10 wt%.

In yet another embodiment, one specific solvent has a solute concentration between about 2 wt% - 40 wt%.

In yet another embodiment, one specific solvent has a tertiary balance to keep one specific solvent or solvent system as a single liquid phase.

In yet another embodiment, the solvent the alkanolamine has a weight percentage between 25 wt% and 40 wt% and is selected from group comprising N-methyldiethanolamine (MDEA), 2-amino-2methyl-l-proponal (AMP); the reactive amines have a weight percentage between 10 wt% and 25 wt% and is selected from group comprising comprising piperazine, N aminoethylpiperazine (AEP); and the glycol has a weight percentage between 10 wt% and 25 wt%.

In yet another embodiment, the solvent the alkanolamine has a weight percentage between 30 wt% and 40 wt% and is selected from group comprising N-methyldiethanolamine (MDEA), 2-amino-2methyl-l-proponal (AMP); the reactive amines have a weight percentage between 10 wt% and 18 wt% and is selected from group comprising comprising piperazine, N aminoethylpiperazine (AEP); and the glycol has a weight percentage between 15 wt% and 20 wt%.

In yet another embodiment, the solvent the alkanolamine has a weight percentage between 32 wt% and 35 wt% and is selected from group comprising N-methyldiethanolamine (MDEA), 2-amino-2methyl-l-proponal (AMP); the reactive amines have a weight percentage between 11 wt% and 15 wt% and is selected from group comprising comprising piperazine, N aminoethylpiperazine (AEP); and the glycol has a weight percentage between 18 wt% and 20 wt%.

In yet another embodiment, the solvent the alkanolamine has a weight percentage between 25 wt% and 40 wt%; the reactive amines have a weight percentage between 10 wt% and 25 wt%; and the glycol has a weight percentage between 10 wt% and 25 wt%.

In yet another embodiment, the solvent the alkanolamine has a weight percentage between 30 wt% and 40 wt%; the reactive amines have a weight percentage between 10 wt% and 18 wt%; and the glycol has a weight percentage between 15 wt% and 20 wt%.

In yet another embodiment, the solvent the alkanolamine has a weight percentage between 32 wt% and 35 wt%; the reactive amines have a weight percentage between 11 wt% and 15 wt%; and the glycol has a weight percentage between 18 wt% and 20 wt%.

In yet another embodiment, the solvent the alkanolamine has a weight percentage between 25 wt% and 40 wt%; the reactive amines have a weight percentage between 10 wt% and 25 wt%; and the sulfolane has a weight percentage between 10 wt% and 25 wt%.

In yet another embodiment, the solvent the alkanolamine has a weight percentage between 30 wt% and 40 wt%; the reactive amines have a weight percentage between 10 wt% and 18 wt%; and the sulfolane has a weight percentage between 15 wt% and 20 wt%.

In yet another embodiment, the solvent the alkanolamine has a weight percentage between 32 wt% and 35 wt%; the reactive amines have a weight percentage between 11 wt% and 15 wt%; and the sulfolane has a weight percentage between 18 wt% and 20 wt%.

In another embodiment, a method of removing C0₂ from a gaseous stream including: contacting a gaseous stream with a solution wherein the solution is formed by combining: alkanolamines, a reactive amine , an carbonate salt, poly ethylene glycol and water; whereby the contact removes C0₂ from the gaseous stream; and regenerating the solution. The concentrations may be limited by the solubility of the components at a temperature and contact of the exhaust gaseous stream with one specific solvent removes C0₂ from the gaseous stream; and regenerating the solution.

The regenerating may include heating C0₂-rich solution, which may occur at a temperature of approximately 90 C - 130 C, approximately 110 C. An additive such as an antifoaming agent, an antioxidant, a corrosion inhibitor (e.g. vanadium oxide or a chromate), a flocculation aid, or a mixture of two or more additives may be included as part of the solution.

In another embodiment, the method of removing C0₂ from a gaseous stream may further include applying a water wash system, wherein the water wash system collects the volatile alkanolamine and reactive amine from treated gaseous stream. The regeneration of the solution may occur in a vacuum stripper column, and the solution may be returned to contact with the gaseous stream after regeneration.

Other components of a gaseous stream, such as COS may also be removed by the method of this disclosure. The gaseous stream may be from a coal-fired power plant, or it may be flue gas, natural gas, hydrogen gas, synthesis gas or a waste gas stream.

Fig. 2 is a schematic diagram of an apparatus for removing acidic gases especially C0₂. As shown in Fig. 2, gas is allowed to enter to an absorption tower 1 through a C0₂ - containing gas-feed. In a packed portion, the gas placed in the absorption tower 1 is brought into contact in a counter flow with a C0₂ absorbent liquid fed from 3, and C0₂ is absorb and removed from the gas by the absorbing liquid, and the resultant gas is discharge from the top as treated gas. The absorbent liquid fed to the absorption tower 1 absorb C0₂, and is led to heat exchanger and heated and led to a regeneration tower 4. In the regeneration tower 4, the absorbent liquid flows through a packed portion towards the lower portion of the tower. During this time, C0₂ is removed to regenerate the absorbent liquid. The regenerated absorbent liquid is led by a pump to the heat exchanger and fed back to the absorption tower 1 through an absorbent liquid feed inlet line 3.

On the other hand, in the upper portion of the regeneration tower 4, the C0₂ removed from the absorbent liquid is brought into contact with a reflux water, and cooled by a regeneration tower reflux condenser and, in a reflux drum, the C0₂ separated from the reflux water formed by condensing water vapor accompanying the C0₂, and led to a C0₂ recovery step. The reflux water is fed by a reflux water pump to the regenerator tower 4. This embodiment briefly describes an overview of the C0₂ capture process description.

Illustrative Examples and Proposed Theory

Heat to produce steam to maintain driving force for C0₂, For the C0₂, to be transferred from the liquid to the gas phase there needs to be driving force on the basis of partial pressure. Thus, steam acts in such a way as to provide this driving force so that the mass transfer of C0₂ from the liquid to the gas phase is enhanced. This also has energy associated with it, which contributes to the overall reboiler duty. This can be obtained by finding out the amount of water associated with the pure C0₂ steam produced as this energy in the form of water is lost and needs to be provided by the reboiler. The stripping heat consists of the following:

QT ^~ Qsens ^~*^~ Qdes ^~*^~ Qstrip

Sensible heat of C0₂ rich solvent to raise the stripper temperature

One specific solvent loaded with C0₂ in the absorber may be heated up to stripper temperature for the regeneration of C0₂. One specific solvent stream can be pre -heated in the lean-rich cross heat exchanger and then additional heat may be used to maintain the temperature of one specific solvent in the stripper.

SC_PAT

Qsens

rich lean ' amine

The contributing factors to the sensible heat are solvent flow, specific heat capacity of one specific solvent and the temperature increase. Thus, the only parameter that can be varied is one specific solvent flow which further depends on the concentration of one specific solvent and one specific solvent loadings. This can be decreased by circulating less solvent and maintaining the same C0₂ production rate. This is checked by means of comparing the Net Capacity of a solvent which is defined as the difference in the loading at the absorption and desorption conditions.

Heat of Desorption of C0₂ The C0₂ which is reversibly bound to one specific solvent needs to be regenerated. The heat of desorption is equivalent to the heat of absorption.

Heat to produce steam to maintain driving force for C0₂

For the C0₂ to be transferred from the liquid to the gas phase there needs to be driving force in the basis of the partial pressure. Thus steam acts in such a way as to provide the driving force so that the mass transfer of C0₂ from the liquid to the gas phase is enhanced. This also has energy associated with it, which contributes to the overall reboiler duty. This can be obtained by finding out the amount of water associated with the pure C0₂ steam produced as this energy in the form of water is lost and needs to be provided by the rebuilder. The stripping heat consists of the following: a strip

Where Η^ζ_α stands for heat of vaporization if water and P_C*₀₂ is the partial pressure of

C0₂ that would be equilibrium with the rich solution at the bottom of the absorber. Thus, finding EXAMPLES

The disclosure will be further described in connection with the following examples, which are set forth for purposes of illustration only.

Table 1 As the rate activator for the C0₂ absorption is piperazine and its derivative, the limitation with piperazine is its high volatility. It has highest reaction kinetics among its derivatives. It is white crystals which need more water to foam a clear solutions or need Polyethylene glycol to solubilize it. But because of the high volatility the loss of the piperazine is high and to minimize the volatility loss in the solvent, piperazine component is partly or completely replaced by rate activator such as N-2-hydroethyl piperazine whose vapor pressure is 99.7% less than piperazine.

Example 2

Below is the composition and characteristics of another exemplary solvent. Density measurement

The densities of were measured using a 25 x 10 m' (at 298 K) Gay-Lussac pycnometer. For each run, the pycnometer containing the solvent solution was put in a constant temperature bath. The bath temperature was controlled within ± 0.1 K of the desired temperature level using a circulator temperature controller. Once the solution reached the desired temperature, it was weighed to within ± 0.0001 g with an analytical balance. Each reported density data is the average of at least three measurements. Viscosity measurement

The viscosities of solutions were measured using Cannon Fenske Viscometer. For each viscosity measurement, the temperature was controlled within ± 0.1 K of the desired level with a circulator temperature controller. The viscometers containing samples were immersed in a thermostatic bath and allowed to equilibrate to the set point temperature for at least 15 min. Later, the efflux time of samples was measured manually with a digital stopwatch having an accuracy of 0.01 s. The efflux time is measured by allowing meniscus to pass between two specific marks. The kinematic viscosity was obtained by multiplying efflux time in seconds with the respective viscometer constant. The dynamic viscosity of the samples is calculated by multiplying the kinematic viscosity values with their corresponding density values. Each viscosity data is the average of at least three measurements.

Density and viscosity of SI:

FIG. 3 describes viscosity in mPa.sec and density in kg/m³ (on Y-axis) w.r.t. temperature °C (on X-axis) for the solvent Si. It is observed that viscosity and density decreases with the increase in temperature.

VLE of Si These measurements can determine the relationship between partial pressure of C0₂ and the subsequent loading of the solvent at different temperatures. This data can be used to do a first assessment of the solvent performance.

Kinetics Experiments Resu ts

Mass%

MDEA 25

Ethylene Glycol 20

Piperazine 15

K₂C0₃ 5 35

Rate v/s C0₂ partial pressure

1.2GE-G5

" l.OOE-05

J. 8.00E-06

6.00E-06

4.00E-06

¾ 2.00E-06

O.OOE-i-00

5 10 15 20

C0₂ partial pressure (kPa)

T = 40 C

Specific rate of absorption increases with CO2 partial pressure.

Below is the composition and characteristics of another exemplary solvent. VLE data for solvent S2

(MDEA + PZ + Tetrahydrothiophenedioxide (SULFOLANE) + water (and K2C03)) (48+2+10+40 wt%, respectively)

254.35 0.790 677.88 0.946 855.13 0.894

496.29 0.934 856.09 1.020 1082.87 0.996

622.43 0.997 955.89 1.087 1127.33 1.062

756.84 1.032 1355.41 1.120

955.89 1.110

VLE data for (MDEA + PZ + SULFOLANE + (H20 and K2C03)) (45+5+10+40 wt%, respectively)

VLE data for (MDEA + PZ + SULFOLANE + water(and K₂C0₃)) (42+8+10+40wt%, respectively)

T=313K T=323K T=333K

^aco₂ PcoJ Pa ^aco₂

1.24 0.236 5.38 0.321 16.80 0.264

16.18 0.503 49.49 0.567 65.72 0.455

94.38 0.750 101.33 0.671 174.93 0.615

192.78 0.855 145.10 0.738 326.32 0.805

223.33 0.895 274.27 0.848 497.35 0.898

465.28 1.004 332.93 0.860 670.47 0.936

599.69 1.082 545.93 0.973 833.25 0.997

777.53 1.144 779.60 1.075 1095.73 1.069

976.05 1.169 984.32 1.130 1164.45 1.091

1013.27 1.182

Claims

1. A solvent for recovery of carbon dioxide from gaseous mixture, comprising:

(a) an alkanolamine,

(b) reactive amines,

(c) a carbonate buffer,

wherein one specific solvent contains less than about 75% by weight of water and has a single liquid phase.

2. The solvent as claimed in Claim 1, further comprising a glycol.

3. The solvent as claimed in Claim 2, wherein the glycol is poly ethylene glycol.

4. The solvent as claimed in Claim 1, further comprising a sulfolane.

5. The solvent as claimed in Claim 2, wherein the glycol is selected from the group consisting of monoethylene glycol (EG), Diethylene Glycol (DEG), Triethylene Glycol, Tetraethylene Glycol, Methoxytriglycol (MTG). Other physical solvent used as a solvent component are Sulfolane, N-Methyl-2-Pyrrolidone (NMP).

6. The solvent as claimed in Claim 1 or 3, the solvent is 41ess than about 30% by weight of water.

7. The solvent as claimed in Claim 1 or 3, wherein the carbonate buffer is a potassium carbonate buffer.

8. The solvent as claimed in Claim 1, wherein the promoter is 2% and 30% wt percent.

9. The solvent as claimed in Claim 1 or 3, wherein the alkanolamine is comprises at least one amine of the formula (I), (II), (III) where x and y respectively satisfy relationship: 1 less than or equal to 5 and 2. less than or equal to 10; and R¹, R², R³, and R⁴ represent— QH_jO_kNi (where i=0 to 10, j=l to 21, k=0 to 5, and 1=0 to 5).

10. The solvent as claimed in Claim 1 or 3, wherein the alkanolamine is selected from group comprising N-methyldiethanolamine (MDEA), 2-(2-aminoethoxy)ethanol,

Aminoethylethanolamine (AEEA), 2-amino-2methyl-l-proponal (AMP), 2-(ethyamino)-ethanol (EAE), 2-(methylamino)-ethanol (MAE), 2-(diethylamino)-ethanol (DEAE), diisopropanolamine (DIP A), methylaminopropylamine (MAP A), 3-aminopropanol (AP), 2,2-dimethyl-l,3- propanedi amine (DMPDA), 3-amino-l-cyclohexylaminopropane (ACHP), diglycolamine (DGA), l-amino-2-propanol (MIPA), 2-methyl-methanolamine (MMEA), diethyl ethanol amine or any combinations thereof at concentration ranging from about 20 wt % to about 45 wt %. The solvent as claimed in claim 1 , wherein the reactive amine is selected from group comprising piperazine, N-aminoethylpiperazine (AEP), N-methylpiperazine, 2-methylpiperazine, 1- ethylpiperazine, l-(2-hydroxyethyl) piperazine, 2,5-dimethylpiperazine , l-Amino-4-Methyl Piperazine and any combinations thereof.

11. The solvent as claimed in Claim 1 , wherein the reactive amine is greater than 6% by weight and buffers the solution to a pH of between about 12 and 14 in the absence of C0₂.

12. The solvent as claimed in Claim 1, wherein

(a) the alkanolamine has a weight percentage between 25 wt% and 40 wt%_selected from group comprising N-methyldiethanolamine (MDEA),2-amino-2methyl-l- proponal (AMP),

(b) reactive amines have a weight percentage between 10 wt% and_25 wt%, selected from group comprising comprising piperazine, N aminoethylpiperazine (AEP),

(c) glycol has a weight percentage between 10 wt% and_20 wt%.

13. The solvent as claimed in Claim 1, wherein (a) the alkanolamine has a weight percentage between 30 wt% and 40 wt%_selected from group comprising N-methyldiethanolamine (MDEA),2-amino-2methyl-l- proponal (AMP)

(b) the reactive amines have a weight percentage between 10 wt% and 18 wt%, selected from group comprising comprising piperazine, N aminoethylpiperazine (AEP)

(c) the glycol has a weight percentage between 15 wt% and 20 wt%

14. The solvent as claimed in Claim 13, wherein the glycol is poly ethylene glycol.

15. The solvent as claimed in Claim 3, wherein

(a) the alkanolamine has a weight percentage between 25 wt% and 40 wt%_selected from group comprising N-methyldiethanolamine (MDEA), 2-amino-2methyl-l- proponal (AMP),

(b) reactive amines have a weight percentage between 10 wt% and_25 wt%, selected from group comprising piperazine, N aminoethylpiperazine (AEP),

(c) the sulfolane has a weight percentage between 10 wt% and_20 wt%.

16. The solvent as claimed in Claim 1, wherein

(a) the alkanolamine has a weight percentage between 32 wt% and 35 wt%_selected from group comprising N-methyldiethanolamine (MDEA),2-amino-2methyl-l- proponal (AMP),

(b) reactive amines have a weight percentage between 11 wt% and 15 wt%, selected from group comprising comprising piperazine, N aminoethylpiperazine (AEP),

(c) poly ethylene glycol has a weight percentage between 18 wt% and 20 wt%.

17. A method for removing C0₂ from a stream, comprising the steps of:

(a) contacting the stream with a solvent having an alkanolamine, rate activator amines, glycol or sulfanone, and a carbonate buffer;

(b) allowing one specific solvent to absorb C0₂ at a temperature ;

(c) regenerating one specific solvent from heating one specific solvent greater than 80.

18. The method as claimed in Claim 17, wherein the stream has a temperature between 40 C to 65 C.

19. The method as claimed in Claim 17, wherein the alkanolamine compounds of the formula (I) include monoethanolamine (MEA), methyldiethanolamine (MDEA), diethanolamine (DEA), triethanolamine (TEA), diisopropanolamine (DIP A), 2-amino-l-propanol (AP), 2-amino- 2-methylpropanol (AMP), ethyldiethanolamine (EDEA), 2-methylaminoethanol (MEA), 2- ethylaminoethanol (EAE), 2-n-propylaminoethanol, 2-nbutylaminoethanol (n-BAE), 2-n pentylaminoethanol, 2-isobutylaminoethanol (IBAE), 2-dimethylaminoethanol (DMAE) and 2- diethylaminoethanol (DEAE), alkanolamine compounds of the formula (II) include 2,3- diaminopropionic acid (DAP A) and glycine and alkanoamine compounds of the formula (III) include 1,2 ethylenediamine.

20. The solvent as claimed in Claim 17, wherein

(c) the glycol has a weight percentage between 18 wt% and 20 wt%.

21. The solvent as claimed in Claim 17, wherein

(c) the sulfolane has a weight percentage between 10 wt% and_20 wt%.

22. A method for removing C02 from a stream, comprising the steps of: (a) contacting the stream with a solvent having components amine, glycol, reactive amine, and a carbonate buffer, wherein the solvent contains less than about 75% by weight of water, (a) allowing the solvent to absorb C02 at a temperature, and (b) regenerating the solvent from heating the solvent greater than 80 C, wherein the stream has a temperature between 40 C to 65 C, and the regeneration is under a pressure between about 0.01 and 30 bar.

23. The method as claimed in claim 21, wherein the amine is hindered amine.