Patent Application
20150367281
The present invention is directed to an absorbent solution for absorbing an acidic gas, such as carbon dioxide, from a gas stream and a process for removing acidic gas from a gas stream.
Reference to any prior art in the specification is not, and should not be taken as, an acknowledgment or any form of suggestion that this prior art forms part of the common general knowledge in Australia or any other jurisdiction or that this prior art could reasonably be expected to be ascertained, understood and regarded as relevant by a person skilled in the art.
Waste gas emissions are of significant concern, and the presence of certain gaseous constituents in a waste gas stream can result in air pollution. There is significant research into methods for treating waste gas streams to remove these gaseous constituents from waste gas streams. Carbon dioxide (CO2) emissions, in particular, attract a great deal of attention and the discussion of waste gas emissions that follows will largely be in respect of carbon dioxide. However, the skilled addressee will appreciate that much of this discussion is also applicable to other waste gases.
There is growing pressure for stationary producers of greenhouse gases to dramatically reduce their atmospheric emissions. Of particular concern is the emission of carbon dioxide (CO2) into the atmosphere. One method of reducing atmospheric CO2 emissions is through its capture and subsequent storage in geological or deep sea reservoirs.
The process for capturing CO2 from power station or combustion device flue gases is termed post combustion capture. In post combustion capture, the CO2 in flue gas is first separated from nitrogen and residual oxygen using a suitable solvent in an absorber. The CO2 is then removed from the solvent in a process called stripping (or regeneration), thus allowing the solvent to be reused. The stripped CO2 is then liquefied by compression and cooling, with appropriate drying steps to prevent hydrate formation. Post combustion capture in this form is applicable to a variety of stationary CO2 sources including power stations, steel plants, cement kilns, calciners and smelters.
Aqueous amine solutions and alkanolamine solutions in particular, have been investigated as solvents in post combustion CO2 capture. The capture process involves a series of chemical reactions that take place between water, the amine and carbon dioxide. Amines are weak bases, and may undergo acid-base reactions. Once dissolved into the amine solution, the aqueous CO2 reacts with water and the neutral form of the amine react to generate carbonic acid (H2CO3), aqueous bicarbonate (HCO3−) ions and aqueous carbonate (CO32−) ions, according to the generally acknowledged equations described below:
CO2+2H2OHCO3−+H3O+ (equation 1)
CO2+OH−HCO3− (equation 2)
CO32−+H3O+HCO3−+H2O (equation 3)
HCO3+H3O−H2CO3+H2O (equation 4)
OH−+H3O+2H2O (equation 5)
RaRbRcN+H3O+RaRbRcNH+ (equation 6)
If the amine contains a primary (RaRbNH, Rb═H) or secondary amine (RaRbNH, Rb≠H), an additional reaction pathway becomes available, where carbon dioxide and the primary or secondary amine react to generate a carbamate (RaRbNCoo−). The carbamate may also then participate in acid-base chemistry, according to the generally acknowledged reactions described below. Tertiary amines (RaRbRcN, Ra, Rb, Rc≠H) cannot form carbamates.
CO2+RaRbNH+H2RaRbNCOO−+H3O+ (equation 7)
RaRbNCOO−+H3O+RaRbNCOOH (equation 8)
It is generally acknowledged that the molar absorption capacity of an aqueous amine solution, as measured by the number of moles of CO2 absorbed per mole of amine functionality in solution (a), is dependent upon the pH equilibria that operate in the amine solution and the formation of carbamate species.
Carbamate formation by primary and secondary amines is a direct reaction between the amine nitrogen and CO2. This reaction consumes two moles of amine per mole of CO2 absorbed. One mole is amine that is converted to carbamate, and the second is amine that accepts the proton released by carbamate formation. Carbamate is also a base, as illustrated by the reaction of equation 8 to form carbamic acid. However, it is a much weaker base than an amine and as such does not contribute as a proton acceptor at typical CO2 absorption conditions. The stability of the carbamate species is influenced only weakly by temperature (the reaction enthalpy is small).
CO2 desorption is achieved by heating of an aqueous amine solution containing CO2. The two major effects of heating are to reduce the physical solubility of CO2 in the solution, and to reduce the pKa of the amine resulting in a concomitant reduction in pH and in CO2 absorption capacity, the net effect of which is CO2 release. The extent of the reduction in pKa is governed by the enthalpy of the amine protonation reaction which in turn is governed by the amine chemical structure. All the other reactions, including carbamate formation, have small reaction enthalpies and are insensitive to temperature. Typically, the enthalpy of amine protonation is four to eight times larger than the enthalpies of the carbonate reactions and two to four times larger than the enthalpy of carbamate formation. It is the lowering of the pH upon heating that drives the reversal of carbamate and carbonate/bicarbonate formation during desorption, rather than any significant reduction in stability.
The cyclic capacity (αcyclic) of an aqueous amine solution is defined as the moles of CO2 that can be absorbed and released per mole of amine by cycling the absorbent between low temperature (αrich) and high temperature (αlean): αcyclic=αrich−αlean. In terms of chemistry, this cyclic capacity is primarily governed by the change in amine pKa with temperature. The larger this cyclic capacity, the more efficient the amine. 30 wt % monoethanolamine (MEA, HO—CH2—CH2—NH2), which is currently employed in industrial CO2 capture, possesses an undesirable cyclic capacity of approximately αcyclic=0.11 (40° C.-80° C.)
In summary, there exists a relationship between the change in amine pKa as a function of temperature, and the cyclic capacity of CO2 absorption and release of an aqueous amine.
Identification of the problem with CO2 absorption cyclic capacity has prompted efforts aimed at seeking amines with improved cyclic capacities. However, amines used for industrial CO2 capture that achieve larger CO2 cyclic absorption capacity than MEA have poor rates of CO2 absorption. Slow CO2 absorption rates are undesirable because to achieve the requisite absorption of CO2 longer gas-liquid contact times are required which means larger absorption columns and greater capital cost. The benefits gained through increased cyclic capacity are thus offset by the disadvantages associated with decreased rates.
Amines such as MEA also suffer from oxidative and thermal degradation due to exposure to molecular oxygen in flue gas, and heating to release absorbed CO2. This degradation requires ongoing reclamation and replenishment of the absorbent solution at considerable cost.
Amines such as MEA are also limited in the maximum concentration that can be used due to corrosion and viscosity. MEA is limited to 30 wt % as at higher concentrations it becomes too corrosive for use in contact with carbon steel. Another amine 2-amino-2-methyl-propanol (AMP, HO—CH2—C(CH3)2—NH2), which is also currently employed in industrial CO2 capture, is also limited to around 30 wt % due to high viscosity.
Richner, Energy Procedia 37 (2013) 423-430 discloses an investigation of benzylamine as a potential solvent for carbon dioxide capture and reports some results. We have found as a result of our further work testing benzylamine in a pilot scale CO2 absorption facility, that benzylamine develops a relatively high vapour pressure in aqueous solutions detracting from the advantages reported by Richner. We observed emission of unreacted benzylamine from the absorber column during operation. This emitted benzylamine further reacted with residual CO2 in the gas stream forming a precipitate and blocking the absorber outlet as well as resulting in a reduction in capture performance of the absorbent.
There thus exists a need to identify amines whose aqueous solutions possess improved properties for application in gas capture technologies, such as CO2 capture technologies.
The vapour pressure of benzylamine and/or substituted benzylamine and the solubility of the acid gas (such as CO2) product from their reaction in aqueous solution can be addressed by the addition of a co-solvent.
In one aspect we provide a process for absorbing target acidic gas from a gas stream rich in the target acidic gas comprising contacting the gas stream with an aqueous composition comprising at least one absorbent compound comprising benzylamine and/or substituted benzylamine dissolved in the aqueous composition wherein the aqueous composition comprises a co-solvent which reduces the vapour pressure of the absorbent compound in the aqueous solution.
In one aspect of the invention there is provided an aqueous composition for absorbing target acidic gas from a gas stream rich in the target acidic gas, the aqueous composition comprising at least one absorbent compound comprising benzylamine and/or substituted benzylamine dissolved in the aqueous composition, wherein the aqueous composition comprises a co-solvent which reduces the vapour pressure of the absorbent compound in aqueous solution.
The vapour pressure of benzylamine and/or substituted benzylamine and the solubility of the CO2 product from the reaction with CO2 in aqueous solution can be addressed by the addition of a co-solvent. The role of the co-solvent is to interact with both the non-polar functionality of the benzene ring in benzylamines and the polar solvent water. The interaction with water can be via hydrogen bonding, polar interactions or both.
The co-solvent will typically have both non-polar and polar character and may have functional groups capable of hydrogen bonding.
In a preferred embodiment the Relative Energy Difference solubility parameter (RED) of the co-solvent in each of benzylamine and water is no more than 1.2, preferably no more than 1.1 such as no more than 1. In one set of embodiments the RED of the co-solvents for each of benzylamine and water is in the range of from 0.3 to 1.2 such as 0.3 to 1.1 or 0.3 to 1. In a preferred set of embodiments the RED of the co-solvent in benzylamine is in the range of from 0.4 to 1.2 such as 0.4 to 1.1 or 0.4 to 1 and the RED of the co-solvent in water is in the range of from 0.3 to 1.1, such as 0.4 to 1.1, 0.4 to 0.9 or 0.4 to 0.75
In one set of embodiments the benzylamine and/or substituted benzylamine has an vapour pressure in the aqueous composition in the absence of the co-solvent which is in practice is greater than the theoretical vapour pressure determined by Raoult's law and the co-solvent provides a vapour pressure of no more than said theoretical vapour pressure. The amount of co-solvent may be determined having regard to the extent of reduction in vapour pressure which is required and the Hansen solubility parameters.
The aqueous composition and process comprising the co-solvent preferably maintains a vapour pressure of benzylamine/and or substituted benzylamine in the aqueous solution of below 0.04 kPa at 40° C. In a particularly preferred embodiment the absorbent comprises benzylamine and the aqueous composition and process comprising the co-solvent preferably maintains a vapour pressure of benzylamine in the aqueous solution of below 0.04 kPa at 40° C.
It is particularly preferred, in order to significantly reduce the vapour pressure in solution, that the co-solvent has a boiling point above the acid gas stripping temperature. In the case of CO2 the stripping temperatures may be in the range of 120-150° C. It is preferred where the acid gas is CO2 that the boiling point of the co-solvent is at least 150° C. and more preferably at least 170° C. The co-solvent will generally be thermally stable at the acid gas stripping temperature such as stable at a temperature of at least 150°.
The co-solvent in one set of embodiments is selected from co-solvents having a defined range of values of the Relative Energy Difference solubility parameter (RED) in water and in benzylamine. Relative Energy Difference solubility parameter (RED) is determined using Hansen Solubility Parameters (Charles M. Hansen, Hansen Solubility Parameters—A Users Handbook, 2nd Edition, CRC Press, 2007). The Hansen Solubility Parameters are 3 terms reflecting dispersion (δD), polar (δP) and hydrogen bonding (δH) interactions between solvent and solute molecules. The “distance” (Rα) between the solubility parameters of two different materials (1 and 2) reflects the likelihood that one will be soluble in the other. The smaller the distance the greater the solubility.)
(Ra)2=4(δD2−δD1)2+(δP2−δP1)2+(δH2−δH1)2
If two materials are soluble in each other it is a requirement that Ra be less than R0. R0 is known as the Hansen interaction radius and the ratio Ra/R0 as the Relative Energy Difference (RED).
A RED of <1.0 indicates high solubility, close to 1.0 indicates a boundary condition and >1.0 indicates progressively decreasing solubility. In addition it is preferable for a co-solvent to have large values of δP and/or δH as these reflect the polar and hydrogen bonding characteristics desirable in the co-solvent.
The term hydrocarbyl is used herein to refer to a hydrocarbon substituent group which may be aliphatic or aromatic or comprise both aliphatic and aromatic components.
Examples of suitable classes from which suitable co-solvents may be chosen are selected from the group consisting of aniline and aniline derivatives, glycols and glycol derivatives selected from glycol ethers, glycol esters and glycol ether esters, long chain and aromatic alcohols, amides, esters, phosphates, amines, nitrogen containing heteroaromatics, organic carbonates and organosulfur compounds.
The co-solvents may include glycols and glycol derivatives, particularly glycol mono ethers, glycol di-ethers, glycol ester ethers, glycol monoesters and glycol diesters.
One group of co-solvents are glycols. The glycols may be C1 to C8 alkylene glycols such as ethylene glycol, propylene glycol and butylene glycol; di-alkylene, tri-alkylene and tetra-alkylene glycols such as diethylene glycol and triethylene glycol, tetraethylene glycol, dipropylene glycol and tripropylene glycol; and polyalkylene glycols (preferably of molecular weight 200-600) such as polyethylene glycols (PEGs) including PEGs of molecular weight in the range of from 200 to 600 such as PEG 200 PEG 400 and PEG 600. Specific examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, tripropylene glycol and tetraethylene glycol.
Preferred glycol monoethers and diethers are formed with hydrocarbyl groups of from 1 to 14 carbon atoms which hydrocarbyl groups may comprise aromatic and/or aliphatic groups. More preferred are generally the alkyl ethers of glycols such as mono-(C1 to C6 alkyl) ethers and di-(C1 to C6 alkyl) ethers of glycols selected from mono-(C2 to C4 alkylene) glycols, di-(C2 to C4 alkylene) glycols and tri-(C2 to C4 alkylene) glycols (particularly mono ethylene glycol, di-ethylene glycol and tri-ethylene glycol and mono-propylene glycol, di-propylene glycol and tri-propylene glycol and poly(alkylene glycol) such as polyalkylene glycol of molecular weight 200 to 600 including PEG 200-600). Specific examples of suitable monoethers of glycols and di-ethers of glycols are formed with C1 to C4 alkyl such as selected from the group consisting of diethylene glycol propyl ether, diethylene glycol methyl ether, diethylene glycol diethylene glycol butyl ether, diethylene glycol ethyl ether, tri-propylene glycol methyl ether, 2-phenoxyethanol di-propylene glycol butyl ether.
The glycol ether esters will generally comprise a (C1 to C6 alkyl) ether group and a C1 to C6 alkanoyl ester group of glycols selected from mono-(C2 to C4 alkylene), di-(C2 to C4 alkylene) and tri-(C2 to C4 alkylene) glycols (particularly mono-.di- and tri-ethylene glycol and mono, di- and tri-propylene glycol) and poly(alkylene glycol) particularly polyalkylene glycol of molecular weight 200 to 600 such as PEG 200-600. Specific examples of glycol ether esters may be selected from glycol ether esters comprising a C1 to C4 alkyl ether and a C1 to C4 alkanoyl ester groups such as selected from the group consisting of diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate and dipropylene glycol methyl ether acetate,
The glycol derivative may be a mono-C1 to C6 alkanoyl or di-C1 to C6 alkanoyl ester of glycols selected from mono-(C2 to C4 alkylene), di-(C2 to C4 alkylene) and tri-(C2 to C4 alkylene) glycols (particularly mono-ethylene glycol, di-ethylene glycol, tri-ethylene glycol, mono-propylene glycol, di-propylene glycol, tri-propylene glycol) and poly(alkylene glycol) such as polyalkylene glycol of molecular weight 200 to 600 including PEG 200 to 600. Specific examples of mono and diesters of glycols include monoesters and diesters of glycols formed with C1 to C4 alkanoyl such as selected from the group consisting of propylene glycol diacetate, ethylene glycol dibutyrate and ethylene glycol diacetate.
One preferred class of co-solvents are diethylene glycol mono alkyl ethers and triethylene glycol mono alkyl ethers wherein the alkyl is selected from methyl, ethyl, propyl and butyl and more preferred are diethylene glycol monobutyl ether and diethylene glycol butyl ether acetate.
A further group of co-solvents are selected from the group consisting of aniline and substituted anilines where the substituent may be selected, for example, from the group consisting of one or more C1 to C4 alkyl groups. Specific examples of anilines may be selected from the group consisting of aniline and 2,4-dimethylaniline.
A further group of co-solvents may be selected from the group consisting of aliphatic and aromatic alcohols such as C6 to C14 alcohols selected from aliphatic alcohols, aromatic alcohols, aromatic substituted aliphatic alcohols and aliphatic substituted aromatic alcohols. Specific examples of such alcohols include 1-octanol, 2-octanol, decyl alcohol, benzyl alcohol, 2-ethyl-1-hexanol and 2-methyl-2,4-pentanediol.
A further group of co-solvents is the amides selected from formamides, acetamides and cyclic amides (lactams) which may be C1 to C8 alkyl formamides and C1 to C6 alkyl formamides substituted in the alkyl group by a substituent selected from hydroxyl and C1 to C6 alkoxy. Cyclic amides include 5 and 6 membered cyclic amides optionally substituted by C1 to C6 alkyl, particularly pyrrolidone and N-substituted pyrrolidone such as N—C1 to C4 alkyl pyrrolidone such as N-methylpyrrolidone. Examples of a formamide co-solvent include formamide and methoxyisopropyl formamide. Examples of acetamides include alkylacetamides such as C1 to C6 acetamides, di-(C1 to C6 alkyl) acetamides and alkyl acetamides substituted on said alkyl by a substituent selected from hydroxyl and C1 to C4 alkoxy. Specific examples of acetamides include methoxypropyl acetamide and methoxyisopropyl acetamide.
The co-solvent may be an ester such as an acetate ester formed between an acid selected from C2 to C20 aliphatic acids and alcohols and polyols selected from C1 to C10 hydrocarbyl alcohols and polyols. Example of ester co-solvents are 2-ethylhexyl acetate, ethyl octanoate and methyl oleate.
The co-solvent may be a mono or di-ester if a diacid such as a C4 to C10 di-acid wherein the alcohol portions are C1 to C6 alkanol. An example of such as co-solvents include diethyl succinate, diethyl phthalate, dimethyl phthalate, di-n-butyl phthalate, n-butyl benzyl phthalate and di-n-butyl sabacate.
The co-solvent may be a ketone comprising two hydrocarbyl groups independently selected from C1 to C12 alkyl, C5 to C6 aryl, C6 to C10 aryl substituted alkyl, C6 to C10 alkyl substituted aryl and carbocyclic ketones of from 5 to 6 constituent ring members optionally substituted by C1 to C4 alkyl. Examples of ketones include isobutyl heptyl ketone and acetophenone.
The co-solvent may be a phosphate ester such as a di-(C1 to C8 alkyl) or tri-(C1 to C8 alkyl) phosphate such as trimethyl phosphate or triethyl phosphate.
The co-solvent may be a nitrogen containing heteroaromatic containing from 1 to 3 nitrogen atoms in a 5 or 6 membered heteroaromatic ring, optionally containing one further heteroatom selected from oxygen and sulphur, which may optionally be substituted. Examples of substituents include one or two substituents independently selected from halo (such as chloro) and C1 to C6 alkyl. Examples of heteroaromatic rings include pyrrole, imidazole, pyrazole, triazole, thiadiazole, pyridine, pyrimidine, pyrazine and triazine. More preferred nitrogen containing heteroaromatics include imidazoles and triazoles such as 1,2,3-triazoles and 1,2,4-triazoles. Preferred heteroaromatic are the imidazoles such as imidazole which may be unsubstituted or substituted by one or two C1 to C6 alkyl groups. Still more preferred imidazoles are imidazole and 1,2-dimethyl imidazole. More examples of suitable imidazoles are described later in the specification. Preferred triazoles include 1,2,3-triazole and 1,2,4-triazole, more preferably 1,2,4-triazole. Preferred pyridines include dichloropyridine.
The co-solvent may be an amine such as selected from the group of primary, secondary and tertiary amines wherein the amine may be part of a heterocyclic ring of from 1 to 6 ring members. The nitrogen may be substituted by a substituent selected from C1 to C20 aliphatic and C1 to C6 alkyl substituted by hydroxyl, glycol or PEG of molecular weight 200 to 600. Examples of such compounds may be selected from the group consisting of N-formyl morpholine, diethanolamine, triethanolamine, monoethanolamine and diglycolamine.
The co-solvent may be a substituted carbonate such as a di-C1 to C20 aliphatic corbonate. Examples of such carbonates include 1,2-dodecane carbonate ethylene carbonate, and cyclic carbonates such as propylene carbonate.
The co-solvent may be an organic sulphur compound such as di(C1 to C10 hydrocarbyl) sulfoxides such as DMSO, di(C1 to C10 hydrocarbyl)sulfones and cyclic sulfones such as sulfolane.
The co-solvent may be a phosphoramide such as hexamethylphosphoramide.
Specific examples of preferred co-solvents may be selected from the group consisting of aniline, ethylene glycol 2-ethylhexyl ether, 2,4-dimethylaniline, benzyl alcohol, decyl alcohol, 1-octanol, diethylene glycol propyl ether, 1,2-butylene carbonate, methoxypropyl acetamide, methoxyisopropyl acetamide, diethylene glycol butyl ether acetate, 1,2-hexane carbonate, 2-octanol, 1,2,3-triazole, 2-ethylhexyl acetate, methoxyisopropyl formamide, diethylene glycol ethyl ether acetate, diethyl succinate, 2-ethyl-1-hexanol, diethylene glycol methyl ether, diethylene glycol butyl ether, diethyl succinate, 2-ethyl-1-hexanol, propylene glycol diacetate, ethylene glycol dibutyrate, tetraethylene glycol, 1,2-decane carbonate, diethylene glycol ethyl ether, 1,2-dodecane carbonate, tripropylene glycol methyl ether, ethylene glycol diacetate, triethyl phosphate, hexamethylphosphoramide, dipropylene glycol methyl ether acetate, 1,2-dimethyl imidazole, N-formyl morpholine, acetophone, di-n-butyl phthalate, N-methyl-2-pyrrolidinone, ethyl octanoate, dimethyl phthalate, diethyl phthalate, tri-n-butyl phosphate, 2-methyl-2,4-pentanediol, tripropylene glycol, benzonitrile, dipropylene glycol butyl ether, diethanolamine, n-butyl benzyl phalate, triethylene glycol, dimethyl sulfoxide, triethanolamine, iso-butyl heptyl ketone, methyl oleate, trimethyl phosphate, 2-pyrrolidinone, di-n-butyl sebacate, 2-phenoxyethanol, propylene glycol, sulfolane, toluene diisocyanate, diethylene glycol, monoethanolamine, ethylene glycol, propylene carbonate, diglycolamine, dipropylene glycol, ethylene carbonate and formamide.
In one set of embodiments the co-solvent comprises at least one selected from the group consisting of cyclic amides, glycols, sulfolane and nitrogen containing heteroaromatics, particularly imidazole, triazoles and pyridine wherein said heteroaromatics are optionally substituted with one or two substituents independently selected from C1 to C6 alkyl and chloro.
In one set of embodiments the co-solvent is selected from the group consisting of ethylene glycol, imidazole, 1,2-dimethylimidazole, 1-methyl-2-pyrrolidone, dichloropyridine, sulfolane and 1,2,4-triazole.
In one embodiment alkanolamine gas absorbents are only present in combination with other co-solvents. The co-solvent component preferably does not include alkanolamine acid gas absorbents such as MEA, DEA or mixtures thereof.
The optimum concentration of co-solvent in the composition will depend on the concentration of benzylamine and/or substituted benzylamine and the specific absorbent used. The co-solvent will typically be used in amounts in the range of from 1% to 20% by volume based on the volume of the aqueous composition.
In one set of embodiments the volume ratio of co-solvent:bezylamine and/or substituted benzylamine is in the range of from 1:20 to 1:1 and more preferably from 1:10 to 1:1. Benzylamine and or substituted benzylamine is preferably present in an amount of 1% to 50% v/v of the composition, preferably 10% to 50% v/v and most preferably benzylamine is present in 10% to 50% v/v of the aqueous composition.
The benzylamine and/or substituted benzylamine may be one or more compound of formula (1):
wherein R1 to R5 are each independently selected from the group consisting of: H, hydroxyl, alkyl hydroxyl, alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, substituted or unsubstituted carbonyl, aldehyde, substituted or unsubstituted carboxylate, substituted or unsubstituted ester, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted carboxamide, substituted or unsubstituted imine, NR6R7, N═CR8R9, and halo; and
R6 and R7 are each independently selected from the group consisting of: H, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, and substituted or unsubstituted C2 to C20 alkynyl;
wherein R8 and R9 are independently selected from the group consisting of H, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, and substituted or unsubstituted C2 to C20 alkynyl substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, substituted or unsubstituted carbonyl, aldehyde, substituted or unsubstituted carboxylate, substituted or unsubstituted ester, substituted or unsubstituted alkoxy, substituted or unsubstituted carboxamide, substituted or unsubstituted imine, NR6R7, and halo; and
when any of R1 to R5 is a substituted C1 to C20 alkyl, the substituted C1 to C20 alkyl is selected from the group consisting of: haloalkane, alkylsulfide, hydroxyalkyl, alkyl thiol, alkyl phosphine, alkyl phosphate, alkyl phosphonate, alkyl ether, alkyl alkanoate, alkyl hydroperoxide alkyl peroxide, alkyl cyanate, alkyl isocyanate, alkyl nitrate, alkyl cyanide, alkyl amide, alkyl imine, alkyl imide, alkyl azide, alkyl diazine, and alkyl nitrite.
The compound of formula (1) may be benzylamine (where R1 to R7 are all hydrogen) or may be a substituted benzylamine where preferably at least one of R1 to R7 (preferably at least one of R1 to R5) comprise a functional group having one or more atoms capable of hydrogen bonding in an aqueous composition where the hydrogen bonding atoms are spaced from the benzylamine group by at least one carbon atom. Where the absorbent comprises a substituted benzylamine it is preferred that no more than 3 of R1 to R7 (preferably at least one of R1 to R5) comprise a functional group having one or more atoms capable of hydrogen bonding in an aqueous composition where the hydrogen bonding atoms are spaced from the benzylamine group by at least one carbon atom.
Preferably, the substituted benzylamine comprises the substituent in the para position of the benzylamine (R4 in formula (1)).
Preferably, where the absorbent is a substituted benzylamine no more than one of R1 to R5 is an alkyl amine. In one embodiment, none of R1 to R5 are alkyl amine. Preferably, none of R1 to R5 is an alkyl aryl. Preferably, no more than three, more preferably not more than two and even more preferably no more than one of R1 to R5 comprises a substituted or unsubstituted C1 to C20 alkyl. In another embodiment, no more than three, more preferably not more than two and even more preferably no more than one of R1 to R5 comprises a substituted or unsubstituted C1 to C5 alkyl. Examples of substituted C1 to C5 allyl include substitution with a substituent selected from the group consisting of hydroxyl, thiol, amino, alkoxy and carboxyl.
The group substituted or unsubstituted carbonyl may be acyl such as a hydrocarbyl-carbonyl where the hydrocarbyl may be selected from group consisting of aryl, C1 to C20 alkyl, C2 to C20 alkenyl and C2 to C20 alkynyl.
The group substituted or unsubstituted carboxyl may be carboxyl or hydrocarbyloxycarbonyl wherein the hydrocarbyl is selected from the group consisting of aryl, C1 to C20 alkyl, C2 to C20 alkenyl and C2 to C20 alkynyl.
The group substituted or unsubstituted ester may be an acyloxy wherein the group acyl is hydrocarbyl-carbonyl where the hydrocarbyl may be selected from group consisting of aryl, C1 to C20 alkyl, C2 to C20 alkenyl and C2 to C20 alkynyl.
More preferably at least one of R′ to R5 is a group capable of hydrogen bonding selected from the group consisting of hydrox-C1 to C4 alkyl (such as hydroxymethyl, 2-hydroxyethyl. 2-hydroxypropyl, 3-hydroxypropyl), carboxyl, carbamoyl, (C1 to C4 alkyl)carbamoyl (such as N-methylcarbamoyl and N-ethylcarbamoyl), di-(C1 to C4 alkyl)carbamoyl (such as N,N-dimethylcarbamoyl and N,N-diethylcarbamoyl), (C1 to C4 alkoxy)carbonyl (such as methoxycarbonyl and ethoxycarbonyl) and C1 to C4 alkanoyl such as acetyl, C1 to C4 alkyl such as methyl ethyl or propyl substituted with a substituent selected from carboxyl, carbamoyl, (C1 to C4 alkyl)carbamoyl (such as N-methylcarbamoyl and N-ethylcarbamoyl), di-(C1 to C4 alkyl)carbamoyl (such as N,N-dimethylcarbamoyl and N,N-diethylcarbamoyl), (C1 to C4 alkoxy)carbonyl (such as methoxycarbonyl and ethoxycarbonyl) and C1 to C4 alkanoyl (such as acetyl). In one embodiment one of R1 to R5 is said group capable of hydrogen bonding and the others are independently selected from hydrogen and C1 to C4 alkyl.
The substituted benzylamines are particularly useful in absorption of acidic gas in aqueous solution when benzylamine is para-substituted by the substituted alkyl having a group capable of hydrogen bonding. Accordingly, in the compound of Formula (1) it is therefore preferred that the group R4 is selected from the group consisting of carboxyl, (C1 to C4 alkoxy)carbonyl, C1 to C4 alkanoyl, carbamoyl, (C1 to C4 alkyl)carbamoyl, di-(C1 to C4 alkyl)carbamoyl and substituted C1 to C4 alkyl wherein the substituent selected from the group consisting of hydroxyl, thiol, C1 to C4 alkoxy, C1 to C4 alkylthio, amino, C1 to C4 alkylamino, di(C1 to C4 alkyl)amino, carboxyl, (C1 to C4 alkoxy)carbonyl, C1 to C4 alkanoyl, carbamoyl, (C1 to C4 alkyl)carbamoyl and di-(C1 to C4 alkyl)carbamoyl.
Specific examples of benzylamine and/or substituted benzylamine compounds of formula (1), with polar substituents able to hydrogen bond are benzylamine and the substituted benzylamines listed below:
The composition and process of the invention are particularly suited to use of benzylamine and we have found that the co-solvent significantly reduces the vapour pressure problems arising from the systems disclosed by Richner (Energy Procedia 37 (2013) 423-430).
Advantageously, compositions have lower susceptibility to thermal and oxidative degradation than a 30 wt % MEA solution due to the inherent chemical stability imparted by the aromatic ring structure. Preferably the cyclic absorption capacity of the solution for the target gas is comparable to that of a tertiary or sterically hindered amine solution and the rate of absorption of the target gas is comparable to or better than a 30 wt % MEA solution.
The solution is preferably a single phase liquid solution prior to the absorption of the acid gas as well as after the absorption of the acid gas (i.e. no precipitation of the reactants of the absorption process). The absorbent may be dissolved or disperse in one or more solvents. The solvent is typically an organic solvent, water or a combination thereof. The organic solvents are preferably a protic and/or a polar aprotic solvent. Suitable solvents that may be used include, but are not limited to, methanol, ethanol, propenol, glycols, carbonates (e.g. propylene carbonate), N-methyl-2-pyrrolidone, acetonitrile, dimethyl sulfoxide, dioxane, sulfolane, dimethylformamide, pyridine, acetone, dichloromethane, methyl ethyl ketone, chloroform, tetrahydrofuran, ethyl acetate, 2-butanone, toluene.
Ideally the target gas is an acidic gas. Preferably the target gas is selected from the group consisting of CO2, NOx (where x is between 0.5 and 2), SO2, H2S, carbonyl sulphide, carbon disulfide, thiols or a halogen gas, such as Cl2, F2, I2, or Br2. More preferably the target gas is CO2 or SO2. Most preferably the target gas is CO2. In an embodiment a number of target gases may be absorbed from a gas stream using the solution of the present invention, the target gases being selected from various combinations of CO2, NOx, SO2, H2S or a halogen gas, such as Cl2, F2, I2, or Br2.
In the more preferred embodiment the target gas is CO2.
In a set of embodiments the total of the absorbent compound component and water constitute at least 40%, preferably at least 50%, more preferably at least 60%, still more preferably at least 70% and even more preferably at least 80% (such as at least 90%) by weight of the total composition.
Preferably the solution is an aqueous solution. The use of an aqueous solution is advantageous for both economic and environmental reasons. The solvent may also be any protic solvent such as methanol, n-butanol or glycol or polar aprotic solvent such as ethylacetate or dimethylsulfoxide in which the acid gas and amine are jointly soluble. Furthermore, the target gas to be absorbed from the gas stream needs to be at least partially soluble in the solvent, so that the target gas is able to interact with the various constituents of the solution. Many of the gases of interest are at least partially soluble in water. In a preferred embodiment, the solvent comprises a mixture of water and a protic solvent (e.g. water and an alcohol) or water and a polar aprotic solvent. The selection of a co-solvent to replace part of the water as a solvent may influenced by improved characteristics of the co-solvent, resulting in a solvent mixture with increased acidic gas solubility, lower heat capacity or a higher boiling point.
In an embodiment R1 to R5 are each independently selected from the group consisting of: H, hydroxyl, or C1 to C10 alkyl; R6 and R7 are independently selected from the group consisting of H, methyl, or ethyl. More preferably the absorbent compound is benzylamine or a benzylamine derivative. Most preferably the compound is benzylamine.
In one set of embodiments, the benzylamine and/or substituted benzylamine compound is present in the solution in a total amount of at least 1% (such as 1% to 70%) by weight based on the weight of the solution. The compound of formula 1 is preferably present in an amount between 1 wt % and 50 wt %, more preferably 1.5 wt % and 40 wt %, even more preferably between 2 wt % and 30 wt % and even more preferably between 5 wt % and 20 wt % based on the total weight of the solution. In a preferred embodiment, the upper limit of the benzylamine ?and/or substituted benzylamine compound is limited by the concentration which results in the precipitation of the reactants of the absorbent(s) and the absorbed acid gases. The upper limit of the compound of benzylamine and/or substituted benzylamine is preferably 70 wt %, more preferably 65 wt %, even more preferably 60 wt % and yet even more preferably 55 wt % of the total weight of the solution.
The total concentration of acidic gas absorbant compounds including the benzylamine/substituted benzylamine compounds is preferably at least about 10 weight %. More preferably the concentration is at least about 20 weight %. Even more preferably the concentration is at least about 30 weight %. Yet even more preferably the concentration is at least about 40 weight %. Most preferably the concentration is at least about 50 weight % or above 50 weight %.
Advantageously, the solution has a low viscosity and low corrosion potential. This allows the solution to contain the compounds at high concentration while still being able to maintain effective operating conditions. This provides for a solution with a large target gas absorption capacity and target gas absorption rate. Preferably the viscosity of the solution measured at 40° C. is less than 3mPa·s. More preferably, the viscosity of the solution is less than 2.75 mPa·s. Even more preferably, the viscosity is less than 2.5 mPa·s.
The at least one absorbent compound dissolved in the solvent will comprise the compound of formula (1) which may constitute the total of the gas absorbent compound or may be present in solution with other acidic gas absorbent compounds so that the total gas absorbent compounds comprise one or more gas absorbent compounds in addition to the compounds of formula (1). In one embodiment the solution contacted with the gas stream comprises one or more acidic gas absorbing compounds selected from amines and imidazoles in addition to the compound of formula (1). The one or more additional amines may be selected from primary, secondary and tertiary amines.
Examples of suitable amines include primary amines such as monoethanolamine, ethylenediamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-ethanolamine and benzylamine; secondary amines such as N-methylethanolamine, piperazine, piperidine and substituted piperidine, diethanolamine, diglycolamine and diisopropanolamine; and tertiary amines such as N-methyldiethanolamine, and amino acids such as taurine, sarcosine and alanine.
In an embodiment, the solution further includes an additional amine compound, such as a tertiary or sterically hindered amine. The additional amine compound helps to avoid precipitation of the absorbent compound out of solution, which may be an issue at high weight loadings of the absorbent compound, and/or depending on the chemical environment of the solution. Suitable compounds may include for example: 2-amino-2-methyl-1-propanol (AMP), 3-piperidinemethanol, 3-piperidineethanol, 2-piperidinemethanol, 2-piperidineethanol, N-piperidinemethanol, N-piperidineethanol, 2-methylaminoethanol, N,N-dimethylaminoethanol and 3-quinclidinol. In some embodiments it is preferred that the compound is not monoethanolamine, diethanolamine, aminoethylethanolamine, Diglycolamine, piperazine, N-Aminoethylpiperazine, N-(2-hydroxyethyl) piperazine and morpholine
In a further embodiment, the solution comprises an imidazole and more preferably an N-functionalised imidazole. Suitable N-functionalised imidazoles may be found in U.S. Pat. No. 8,741,246, which in incorporated herein by reference.
The suitable N-functionalised imidazoles disclosed in U.S. Pat. No. 8,741,246 are of formula (2):
wherein
R1 is substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C2-20 alkynyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C2-20 heteroalkenyl, substituted or unsubstituted C2-20 heteroalkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted thio, substituted or unsubstituted amino, substituted or unsubstituted alkoxyl, substituted or unsubstituted aryloxyl, silyl, siloxyl, cyano, or nitro; and
R2, R3, and R4 are each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C2-20 alkynyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C2-20 heteroalkenyl, substituted or unsubstituted C2-20 heteroalkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted thio, substituted or unsubstituted alkoxyl, aryloxyl, substituted or unsubstituted amino, cyano, or nitro.
Specific examples of such compounds include the 1-N—(C1 to C20 alkyl) imidazoles such as 1-butyl imidazole
In some, embodiment the solution comprises a combination of N-functionalised imidazoles and one or more amines.
The one or more amines which may be used in addition to the N-functionalised imidazoles may be selected from the group consisting of primary, secondary and tertiary amines including the specific examples of such amines referred to above.
The total wt % of the at least one absorbent compound in solution is preferably at least 20 wt %, more preferably at least 25 wt %, still more preferably at least 30 wt %, even more preferably at least 40 wt % and yet even more preferably at least 50 wt % relative to the total weight of the solution. This component will typically consists of the compound of formula (1) and optionally one or more compounds selected from amines and N-functionalised-imidazoles. The compound of chemical formula (1) preferably comprises at least 1% (e.g. 1% to 70%) more preferably between 1 wt % and 50 wt %, still more preferably between 1.5 wt % and 40 wt %, even more preferably between 2 wt % and 30 wt % and even more preferably between 5 wt % and 20 wt % relative to the total weight of the solution.
In another aspect of the invention there is provided a process for removing a target gas from a gas mixture including: contacting a gas mixture that is rich in target gas with an absorbent solution, as described above, to form a target gas rich solution and a gas mixture that is lean in target gas; and desorbing the target gas from the target gas rich solution. In yet a further set of embodiments there is further provided use of a compound of formula (1) in solution in a solvent at a concentration of at least 20% by weight, based on the total weight of the solution, for absorbing an acidic gas from a gas stream.
In one set of embodiments there is further provided a composition comprising a solution for an acidic gas comprising:
Preferably, the concentration of the absorbed acidic gas is more than two times (and even more preferably five times) the equilibrium concentration when the solution is exposed to air at below the boiling point of the solvent, thus representing the absorbed acidic gas concentration in the solvent during the absorption process as previously described. The background amount of acidic gas, such as CO2, will generally be less than 0.1% by weight based on the total weight of the solution. In one embodiment the absorbed acidic gas will constitute at least 0.2% by weight based on the total weight of the solution on absorption of the gas more preferably at least 1% and still more preferably at least 10% absorbed acidic gas by weight based on the total weight of the solution.
In one embodiment the solution comprises one or more amines in addition to the benzylamine and/or substituted benzylaminecompound which additional amines may, for example, be selected from primary, secondary and tertiary amines optionally including N-functionalised imidazoles such as those of formula (2).
In a set of embodiments the total of the absorbent component and water constitute at least 40%, preferably at least 50%, more preferably at least 60%, still more preferably at least 70% and even more preferably at least 80% (such as at least 90%) by weight of the total composition.
Further aspects of the present invention and further embodiments of the aspects described in the preceding paragraphs will become apparent from the following description, given by way of example and with reference to the accompanying drawings.
The invention relates to the use of an aqueous composition comprising a solution benzylamine, a benzylamine derivative, a benzylamine mixture, a benzylamine derivative mixture, or a combination thereof for absorbing an acid target gas from a gas stream wherein the aqueous composition comprises a co-solvent.
The absorption reactor 102 includes a first inlet 106, a second inlet 108, a first outlet 110, and a second outlet 112, and a gas absorption contact region 114. The first inlet 106 of the absorption reactor 102 is a flue gas inlet through which a CO2 rich flue gas enters the absorption column 102. The second inlet 108 is an absorbent solution inlet through which a CO2 lean absorbent enters the absorption column 102. The CO2 rich flue gas and the CO2 lean absorbent contact in the gas absorption contact region 114. In this region the CO2 in the CO2 rich flue gas is absorbed into the absorbent solution where it is bound in solution to form a CO2 lean flue gas and a CO2 rich absorbent solution.
The absorbent solution includes an benzylamine and/or substituted benzylamine absorbent and a co-solvent. In this particular embodiment, the absorbent molecule is benzylamine, e.g.:
The local environment of the solution may be altered in the absorption column to favour the absorption reaction, e.g. to increase absorption of CO2 into solution where it is bound to the benzylamine. Such alterations of the local environment may include a change in pH, a change in solution temperature, a change in pressure etc. Alternatively, or additionally, the solution may include other compounds which assist in the absorption of CO2. These compounds may alter the affinity or absorption capacity of the benzylamine for CO2, or these compounds may be also absorb CO2.
If additional compounds are added to the absorbent solution in the absorption reactor 102, the process may additionally include means to remove these compounds.
The absorption of CO2 from the CO2 rich flue gas into the absorbent solution results in a CO2 lean gas and a CO2 rich absorbent solution. The CO2 lean gas may still include some CO2, but at a lower concentration than the CO2 rich flue gas, for example a residual concentration of CO2.
The CO2 lean gas leaves the absorption column 102 through the first outlet 110, which is a CO2 lean gas outlet. The CO2 rich absorbent solution leaves the absorption column through the second outlet 112, which is a CO2 rich absorbent outlet.
Desorption reactor 104 includes an inlet 118, a first outlet 120, a second outlet 122, and a gas desorption region 124. The CO2 rich absorbent outlet 112 of the absorption column 102 forms the inlet 118 of the desorption column 104. Desorption of CO2 from the CO2 rich solution occurs in the gas desorption region 124.
Desorption of CO2 from the CO2 rich solution may involve the application of heat or a reduction in pressure to favour the desorption process. Furthermore, additional compounds may be added to the CO2 rich solution to enhance the desorption process. Such compounds may alter the solution environment, for example by changing solution pH or altering another parameter to favour the desorption reaction.
Removal of CO2 from the CO2 rich solution results in the formation of a CO2 gas stream and a CO2 lean absorbent solution. The CO2 lean absorbent solution may still include some CO2, but at a lower concentration than the CO2 rich solution, for example a residual concentration of CO2.
The CO2 gas stream is taken off via the first outlet 120, which is a CO2 outlet. The CO2 lean absorbent solution is taken off via the second outlet 122, which is a CO2 lean absorbent solution outlet. The CO2 lean absorbent is then recycled and fed through the second inlet 108 to the absorption column 102.
The invention will now be described with reference to the following Examples. It is to be understood that the examples are provided by way of illustration of the invention and that they are in no way limiting to the scope of the invention.
Tabulated below in Table 1 are values for the Hansen Solubility Parameters of a number of potential co-solvents with a RED of <1.0. The value for benzylamine in water is also included for reference. For water R0=13.9 and this value was used for the calculations of RED—values for the solubility of both water and benzylamine in co-solvents as the miscibility of benzylamine in water indicates they will share a similar R0 value.
Referring to
The CO2 mass absorption capacity, expressed in kg CO2/kg solvent (water) of several concentrations of benzylamine and a mixture (30 wt % and 50 wt % BA, and 50 wt % BA+10 wt % AMP) were tested at different partial pressures of CO2 in a vapour-liquid-equilibrium (VLE) apparatus including a 160 ml glass vessel, a thermal bath, and a CO2 dosing unit between 40° C. and 80° C. The method was validated by comparing measurements of CO2 absorption by MEA 30 wt % with literature data. Results of this experiment are presented in
We have found as a result of our further work testing benzylamine in a pilot scale CO2 absorption facility, that benzylamine develops a relatively high vapour pressure in aqueous solutions detracting from the advantages reported by Richner. We observed emission of unreacted benzylamine from the absorber column during operation. This emitted benzylamine further reacted with residual CO2 in the gas stream forming a precipitate and blocking the absorber outlet as well as resulting in a reduction in capture performance of the absorbent.
The high vapour pressure of benzylamine observed in the trials may be significantly resuced by inclusion of a volume such as 10% v/v of the composition of a co-solvent such as listed in Table 1.
The mass transfer coefficient of CO2 absorption (Kg, mmol·m−2s−1 kPa−1) in benzylamine and benzylamine mixtures may been measured at 40° C. The CO2 loading (mol CO2/mol amine) of the liquid may also be varied. The measurements are made using a wetted-wall contactor in which the rate of CO2 absorption is measured into a falling liquid film of known surface area at atmospheric pressure. This device mimics the gas-liquid contacting of a packed column. Details of the device and experimental procedure can be found in G. Puxty, et al., Chem. Eng. Sci., 65 (2010), 915-922.
This Example examines the benzylamine vapour pressure generated in an aqueous mixture with a range of co-solvents.
Procedure:
The results of the measurements are shown in Table 2
The results are presented in the column chart in
A number of these compounds can be compared to the Relative Energy Difference (RED) as estimated using the Hansen Solubility Parameters (tabulated previously). The RED value in either benzylamine or water indicates the likely solubility of the compound in each respectively. The percent reduction in benzylamine (BZA) vapour pressure is correlated with the RED for the co-solvents in benzylamine and water in
Mixtures of benzyamine (BZA) and imidazole (IMD) were prepared in aqueous solution at various concentrations with the solutions being saturated in CO2. The presence of precipitates was observed and recorded.
The following Table 3, where indicated by X or O, shows the solutions tested and the results are presented where “O” refers to the absence of precipitate and “X” the presence of precipitate.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013903284 | Aug 2013 | AU | national |
| 2014901053 | Mar 2014 | AU | national |
| 2014905002 | Dec 2014 | AU | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/AU2014/000859 | Aug 2014 | US |
| Child | 14838608 | US |
