AU2013205811B2 - An improved CO2 absorption solution - Google Patents
An improved CO2 absorption solution Download PDFInfo
- Publication number
- AU2013205811B2 AU2013205811B2 AU2013205811A AU2013205811A AU2013205811B2 AU 2013205811 B2 AU2013205811 B2 AU 2013205811B2 AU 2013205811 A AU2013205811 A AU 2013205811A AU 2013205811 A AU2013205811 A AU 2013205811A AU 2013205811 B2 AU2013205811 B2 AU 2013205811B2
- Authority
- AU
- Australia
- Prior art keywords
- absorption
- carbonic anhydrase
- solution
- formulation
- immobilized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 116
- 102000003846 Carbonic anhydrases Human genes 0.000 claims abstract description 61
- 108090000209 Carbonic anhydrases Proteins 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 29
- 238000009472 formulation Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000012546 transfer Methods 0.000 claims description 17
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 14
- 238000012856 packing Methods 0.000 claims description 10
- 150000005323 carbonate salts Chemical class 0.000 claims description 8
- 230000001965 increasing effect Effects 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000007942 carboxylates Chemical group 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 34
- 102000004190 Enzymes Human genes 0.000 abstract description 12
- 108090000790 Enzymes Proteins 0.000 abstract description 12
- 239000012190 activator Substances 0.000 abstract description 9
- 239000011942 biocatalyst Substances 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 116
- 229910002092 carbon dioxide Inorganic materials 0.000 description 107
- 239000000243 solution Substances 0.000 description 80
- 150000001412 amines Chemical class 0.000 description 26
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 18
- 239000001569 carbon dioxide Substances 0.000 description 17
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 12
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- -1 carbamate compound Chemical class 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 7
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 7
- 150000001983 dialkylethers Chemical class 0.000 description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 238000003889 chemical engineering Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 159000000011 group IA salts Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 108010093096 Immobilized Enzymes Proteins 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- OWIUPIRUAQMTTK-UHFFFAOYSA-N carbazic acid Chemical group NNC(O)=O OWIUPIRUAQMTTK-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000004885 piperazines Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- XXJGBENTLXFVFI-UHFFFAOYSA-N 1-amino-methylene Chemical compound N[CH2] XXJGBENTLXFVFI-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940044613 1-propanol Drugs 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- PTHDBHDZSMGHKF-UHFFFAOYSA-N 2-piperidin-2-ylethanol Chemical compound OCCC1CCCCN1 PTHDBHDZSMGHKF-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229940058302 antinematodal agent piperazine and derivative Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004879 molecular function Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical class NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Abstract The present invention relates generally to solutions for absorbing C0 2for extraction and purification of gases, More particularly, it relates to a C02 absorption solution containing a biocatalyst, namely carbonic anhydrase as an activator, to increase C02 absorption rate, It also concerns the use of a biocatalyst, namely carbonic anhydrase, in a CO2 absorption solution to increase the C02 absorption rate of such solution.
Description
AN IMPROVED C02 ABSORPTION SOLUTION FIELD OF THE INVENTION
The present invention relates generally to solutions for absorbing C02for extraction and purification of gases. More particularly, it relates to a C02 absorption solution containing a biocatalyst, namely carbonic anhydrase as an activator, to increase C02 absorption rate. It also concerns the use of a biocatalyst, namely carbonic anhydrase, in a C02 absorption solution to increase the C02 absorption rate of such solution.
BACKGROUND OF THE INVENTION C02 removal from a gas stream may be obtained using chemical and physical absorption processes. Chemical absorption of C02 may be performed with amine based processes and alkaline salt-based processes. In such processes, the absorbing medium reacts with the absorbed C02. Amines may be primary, secondary, and tertiary. These groups differ in their reaction rate, absorption capacity, corrosion, degradation, etc. In alkaline salt-based processes, the most popular absorption solutions have been sodium and potassium carbonate. As compared to amines, alkaline salt solutions have lower reaction rates with C02.
Alkanolamines in aqueous solution are another class of absorbent liquid for carbon dioxide removal from gaseous mixtures. Alkanolamines are classified as primary, secondary, or tertiary depending on the number of non-hydrogen substituents bonded to the nitrogen atom of the amino group. Monoethanolamine (HOCH2 CH2NH2) is an example of a well-know primary alkanolamine. Widely used secondary alkonalamine include diethanolamine ((HOCH2CH2)2NH). Triethanolamine ((HOCH2CH2)3N) and methyldiethanolamine ((HOCH2CH2)2NCH3) are examples of tertiary alkanolamines which have been used to absorb carbon dioxide from industrial gas mixtures. Molecular structures of sterically hindered amines are generally similar to those of amines, except sterically hindered amines have an amino group attached to a bulky alkyl group. For example, 2-amino-2~methyl-1-propanol (NH2-C(CH3)2CH2OH).
With primary and secondary alkanolamines (Pinola et al. Simulation of pilot plant and industrial C02- MEA absorbers, Gas Separation & Purification, 7(1), 1993; Barth et al., Kinetics and mechanisms of the reactions of carbon dioxide with alkanolamines; A discussion concerning the cases of MDEA and DEA, Chemical Engineering Science, 39(12), pp. 1753-1757, 1984) the nitrogen reacts rapidly and directly with carbon dioxide to bring the carbon dioxide into solution according to the following reaction sequence:
(1) where R is an alkanol group. This reaction is the cornerstone of the present invention, as it is the one accelerated by carbonic anhydrase. The carbamate reaction product (RNHCOCT) must be hydrolysed to bicarbonate (HCO3") according to the following reaction:
(2)
In forming a carbamate, primary and secondary alkanolamine undergo a fast direct reaction with carbon dioxide which makes the rate of carbon dioxide absorption rapid. In the case of primary and secondary alkanolamines, formation of carbamate (reaction 1) is the main reaction while hydrolysis of carbamate (reaction 2) hardly takes place. This is due to stability of the carbamate compound, which is caused by unrestricted rotation of the aliphatic carbon atom around the aminocarbamate group. According to US 4,814,104 the overall reaction for the alkanolamines is written as:
(3)
For the sterically hindered amines both reactions 1 and 2 play major roles on the CO2 absorption process. In contrast with the alkanolamines, the rotation of the bulky alkyl group around the aminocarbamate group is restricted in sterically hindered amines. This results in considerably low stability of the carbamate compound. The carbamate compound is thus likely to react with water and forms free amine and bicarbonate ions (reaction 2). Due to the occurrence of reaction 2, only 1 mol of the sterically hindered amine instead of 2 mol of alkanolamine is required to react with 1 mol of CO2. The overall reaction for sterically hindered amines can be written as (Veawab et al., “ Influence of process parameters on corrosion behaviour in a sterically hindered amine- C02 system”, Ind.Eng.Chem.Res., V 38, No. 1; 310-315; 1999; Park et al., Effect of steric Hindrance on carbon Dioxide Absorption into New Amine Solutions: Thermodynamic and Spectroscopic Verification and NMR Analysis, Environ. Science Technol. 37, pp.1670-1675, 2003; Xu, Kinetics of the reaction of carbon dioxide with 2-amino-2-methyl-1 -propanol solutions, Chemical Engineering Science, 51(6), pp.841-850, 1996):
(4)
Unlike primary and secondary alkanolamines, tertiary alkanolamines cannot react directly with carbon dioxide, because their amine reaction site is fully substituted with substituent groups. Instead, carbon dioxide is absorbed into solution by the following slow reaction with water to form bicarbonate (US 4,814,104; Ko, J.J. etal., Kinetics of absorption of carbon dioxide into solutions of N-methyldiethanolamine + water, Chemical Engineering Science, 55, pp.4139-4147,2000; Crooks, J.E. etal., Kinetics of the reaction between carbon dioxide and tertiary amines, Journal of Organic Chemistry, 55(4), 1372-1374,1990; Rinker.E.B. et al., Kinetics and modelling of carbon dioxide absorption into aqueous solutions of N-methyldiethanolamine, Chemical Engineering Science, 50(5), pp.755-768, 1995):
(5)
Physical absorption enables C02 to be physically absorbed in a solvent according to Henry’s law. Such absorption is temperature and pressure dependent. It is usually used at low temperature and high pressures. Typical solvents are dimethylether of polyethylene glycol and cold methanol.
In recent years, a lot of effort has been put to develop new absorption solutions with enhanced C02 absorption performance. The use of sterically hindered amines, including aminoethers, aminoalcohols, 2-substituted piperidine alcohols and piperazine derivatives, in solution to remove carbon dioxide from acidic gases by scrubbing process was the object of a patent in the late 1970 (US 4,112,052). Yoshida et al. (US 5,603,908) also used hindered amines to remove C02 from combustion gases, but mainly focused on reducing the energy consumption from the amines regeneration. Fujii et al. (US 6,274,108) used MEA in a process to absorb C02 from combustion exhaust gases, but were more concerned about the plant design, more specifically storage of the amines and replenishing system. Instead of using amines, Suzuki et al. used various formulations of amino-amides to remove carbon dioxide from gases and absorbent (US 6,051,161).
In literature, some have reported new formulations of absorption solutions for chemical and physical processes. Reports exist about the reduction of corrosion of carbon steel with the use of certain amine compounds (US 6,689,332). These new formulations may imply mixtures of amines (chemical solvent). For instance, patent US 5,246,619 discloses a way of removing acid gases with a mixture of solvents comprising methyldiethanolamine and methylmonoethanolamine. Mixtures of dialkyl ethers of polyethylene glycol (physical solvent) (US 6,203,599), and mixtures of chemical and physical solvents are reported. GB 1102943, for instance, reports a way of removing C02 by using a solution of an alkanolamine in a dialkyl ether of a polyalkylene glycol, while US 6,602,443 reduces C02 concentration from gas by adding tetraethylene glycol dimethyl ether in combination with other alkyl ethers of alkylene glycols. Although US 6,071,484 describes ways to remove acid gas with independent ultra-lean amines, mention is also made that a mixture of amines and physical absorbents can also be used with similar results.
In order to increase the rate of CO2 absorption, especially for aqueous tertiary alkanolamine solutions, promoters have been added to the solutions. Promoters such as piperazine, Ν,Ν-diethyl hydroxylamine or aminoethylethanolamine (AEE), is added to an absorption solution (chemical or physical solvent). Yoshida et al. (US 6,036,931) used various aminoalkylols in combination with either piperidine, piperazine, morpholine, glycine, 2-methylaminoethanol, 2-piperidineethanol or 2-ethylaminoethanol. EP 0879631 discloses that a specific piperazine derivative for liquid absorbent is remarkably effective for the removal of CO2 from combustion gases. Peytavy et al. (US 6,290,754) used methyldiethanolamine with an activator of the general formula hkN-CnHn-NH-Chb-ChfeOH, where n represents an integer ranging from 1 to 4. US 6,582,498 describes a wire system to reduce C02 from gases where absorbent amine solutions and the presence of an activator are strongly suggested. US 4,336,233 relates to a process for removing C02 from gases by washing the gases with absorbents containing piperazine as an accelerator. Nieh (US 4,696,803) relied on aqueous solution of N-methyldiethanolamine and Ν,Ν-diethyl hydroxylamine counter currently contacted with gases to remove CO2 or other acid gases. Kubek et al (US 4,814,104) found that the absorption of carbon dioxide from gas mixtures with aqueous absorbent solutions of tertiary alkanolamines is improved by incorporating at least one alkyleneamine promoter in the solution.
Other ways of enhancing C02 absorption involve ionic liquids, more specifically a liquid comprising a cation and an anion having a carboxylate function (US 2005/0129598). Bmim-acetate and hmim-acetate are cited as examples.
Mention of enzyme utilization for gas extraction can also be found in the literature (US 6,143,556, US 4,761,209, US 4,602,987, US 3,910,780). Bonaventura et al. (US 4,761,209) used carbonic anhydrase immobilized in a porous gel to remove CO2 in an underwater rebreathing apparatus. Carbonic anhydrase can also be used to impregnate membranes used to facilitate C02 transfer into water for similar purposes (US 4,602,987, US 3,910,780). Efforts were made to ensure that the active site of the enzymes fixed on the membranes were in direct contact with the gas phase substrate to increase the activity of the enzymes (US 6,143,556). This patent is the direct continuation of patent US 6,524,843, which claimed a way to remove CO2 from gases with an enzyme, the carbonic anhydrase. This new patent aims at improving the CO2 absorption of the previous patent through the additional use of solvents, increasing the performance of the bioreactor. CO2 transformation may be catalyzed by a biocatalyst. The biocatalyst is preferably the enzyme carbonic anhydrase. CO2 transformation reaction is the following:
(6)
Under optimum conditions, the turnover rate of this reaction may reach 1 x 106 molecules/second (Khalifah,R and Silverman D.N., Carbonic anhydrase kinetics and molecular function, The Carbonic Anhydrase, Plenum Press, New York, pp.49-64, 1991).
SUMMARY OF THE INVENTION
In a first aspect, the present invention provides a formulation for CO2 reactions comprising: (a) a solution comprising: (i) water; and (ii) at least one tertiary amino reaction compound having the formula R3N and enabling reaction (A):
(A); and (b) carbonic anhydrase to catalyze reaction (B):
(B).
In a second aspect, the present invention provides a method for absorption of C02 comprising contacting gaseous C02 with an aqueous C02 absorption solution comprising at least one C02 absorption compound and carbonic anhydrase wherein the carbonic > anhydrase enables at least a 80% increase in C02 transfer rate relative to the same > aqueous C02 absorption solution without the carbonic anhydrase.
I 5 In a third aspect, the present invention provides a method to enhance C02 absorption, * comprising providing carbonic anhydrase within a packed bed reactor; contacting gaseous ) C02 with an aqueous C02 absorption solution comprising at least one C02 absorption compound within the packed bed reactor in the presence of the carbonic anhydrase; and ] operating the packed bed reactor to enable increased C02 transfer rate of at least 80% ^ relative to the same absorption solution without the carbonic anhydrase. I In a fourth aspect, the present invention provides a formulation for absorption of C02 j comprising water and at least one C02 absorption compound comprising a carbonate salt, * the water and the at least one C02 absorption compound forming an alkaline carbonate salt based solution; and carbonic anhydrase to enhance the absorption of C02 into the alkaline carbonate salt based solution.
In a fifth aspect, the present invention provides a formulation for absorption of C02 comprising water, at least one aliphatic C02 absorption compound non-reactive directly with C02, and carbonic anhydrase to enhance the absorption of the C02 into the water.
In a sixth aspect, the present invention provides a formulation for catalysis of the following reaction:
comprising water, at least one reaction compound comprising a cation and an anion having a carboxylate function, the water and the at least one reaction compound forming a solution; and carbonic anhydrase to catalyze the reaction.
One object of the present invention is to provide a CO2 absorption solution with an increased CO2 absorption rate.
In accordance with the present invention, that object may be achieved with a formulation for absorbing CO2 containing water, at least one CO2 absorption compound, and carbonic anhydrase as an activator to enhance the absorption capacity of the CO2 absorption compound. A CO2 absorption compound in accordance with the present invention represents any compound known in the field which is capable to absorb gaseous CO2·
Preferably, the CO2 absorption compound is selected from the group consisting of amines, alkanolamines, dialkylether of polyalkylene glycols and mixtures thereof.
By "amines" (as also in the term "alkanolamines"), it is meant any optionally substituted aliphatic or cyclic amines or diamines.
More preferably, the amines are selected from the group consisting of piperidine, piperazine and derivatives thereof which are substituted by at least one alkanol group.
By "alkanol", as in the terms "alkanol group" or "alkanolamines", it is meant any optionally substituted alkyl group comprising at least one hydroxyl group.
Advantageously, the alkanolamines are selected from the group consisting of monoethanolamine (MEA), 2-amino-2-methyl-l-propanol (AMP), 2-(2- aminoethylamino)ethanol (AEE), 2-amino-2-hydroxymethyl-l ,3-propanediol (Tris), N-methyldiethanolamine (MDEA) and triethanolamine.
The preferred dialkylether of polyalkylene glycols used according to the invention are dialkylether of polyethylene glycols. Most preferably, a dialkylether of polyethylene glycol is a dimethylether of polyethylene glycol.
Another object of the invention is to provide a method to activate a CO2 absorption solution, which comprises the steps of: - contacting gaseous CO2 with an aqueous CO2 absorption solution containing at least one CO2 absorption compound; and - adding carbonic anhydrase to said C02 absorption solution while it is contacted with said gaseous CO2.
Carbonic anhydrase is used as an activator to enhance performance of absorption solutions (for chemical/ physical absorption) for CO2 capture.
Thus, another object of the invention concerns the use of carbonic anhydrase as an activator to increase CO2 absorption rate in an aqueous solution used for CO2 absorption.
The enzyme may be one of the constituents of the absorption solution or it can be fixed to a solid substrate (support) such as packing material onto which the absorption solution, in contact with gaseous CO2, flows.
The present invention aims to achieve at least one of the abovementioned objects.
The objects, advantages and other features of the present invention will be better understood upon reading of the following non-restrictive description of preferred embodiments thereof, given for the purpose of exemplification only, with reference to the accompanying figures and examples.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 represents the performance, with or without using carbonic anhydrase, of absorption solutions comprising MEA, Tris, AMP, AEE, Pz or PEG DME as the CO2 absorption compound; the performance is expressed as the relative CO2 transfer rate of the given solution to the CO2 transfer rate of a MEA solution without carbonic anhydrase, the concentration of the absorption solutions is 1.2 x 10"2 M. FIG. 2 represents the performance, with or without using carbonic anhydrase, of absorption solutions comprising MEA, AMP, MDEA or Tris as the absorption compound; the performance is expressed as the relative C02 transfer rate of the 25 given solution to the C02 transfer rate of a MEA solution without carbonic anhydrase; the concentration of the absorption solutions is 1.44 x 101 M. FIG. 3 represents the performance, with or without using carbonic anhydrase, of absorption solutions comprising MEA or AMP as the absorption compound; the performance is expressed as the relative CO2 transfer rate of the given solution to the C02 transfer rate of a MEA solution without carbonic anhydrase. the concentration of the absorption solutions is 0.87 x 10'1 M.
DESCRIPTION OF PREFERRED EMBODIMENTS
The activation of an absorption solution by carbonic anhydrase may be obtained (1) by directly adding carbonic anhydrase to the absorption solution or (2) by contacting an absorption solution, in contact with a gas phase containing CO2, to a solid support having immobilized carbonic anhydrase.
Carbonic anhydrase enhances performance of absorption solutions by reacting with dissolved C02l maintaining a maximum CO2 concentration gradient between gas and liquid phases and then maximizing CO2 transfer rate.
The following examples present the two ways to activate absorption solutions with carbonic anhydrase.
Example 1
An experiment was conducted in an absorption column. The absorption solution is an aqueous solution of 2-amino-2-hydroxymethyl-1,3-propanediol (0,15% (w/w)). This absorption solution is contacted contercurrently with a gas phase with a C02 concentration of 52,000 ppm. Liquid flow rate was 1.5 L/min and gas flow rate was 6.0 g/min. Gas and absorption solution were at room temperature. Operating pressure of the absorber was set at 5 psig. The column has a 7.5 cm diameter and a 70 cm height. Two tests were performed: the first with no activator, the second with carbonic anhydrase. The concentration of carbonic anhydrase is adjusted to 20 mg per liter of solution.
The results obtained showed that CO2 removal rate is 1.5 time higher in the absorption solution containing carbonic anhydrase. C02 transfer rate was equal to 2.3 x 10‘3 mol/min with carbonic anhydrase.
Example 2 A gas, containing C02 at a concentration of 8% (v/v) is fed to a packed bed reactor containing immobilized carbonic anhydrase. The solid substrate is a polymeric material. The gas is countercurrently contacted to an aqueous absorption solution. Impact of the presence of the immobilized enzyme, as an activator, has been tested for chemical and physical solvents. Selected compounds for absorption solutions are monoethanolamine (MEA), piperazine (Pz), 2-amino-2-methyl-1 -propanol (AMP), 2-(2-aminoethylamino)ethanol (AEE), 2-amino-2, hydroxymethyl-1,3-propanediol (Tris) and dimethyl ether of polyethylene glycol (PEG DME). Solutions were prepared at a concentration of 1.2 x 10"2 M.
Operating conditions were the following: gas flow rate is 3.0 g/min, absorption solution flow rate is 0.5 L/min. Height of packing with immobilized enzyme 75 cm. Operating pressure is 1.4 psig.
Performance of absorption solutions are shown in Figure 1. Performance is expressed as a relative C02 transfer rate:
From Figure 1, it can be observed that carbonic anhydrase enhanced the C02 absorption of both chemical and physical absorption solutions.
Example 3 A gas, containing 8% of CO2 (v/v) is fed to a packed bed reactor containing immobilized carbonic anhydrase. The solid substrate is a polymeric material. The gas is countercurrently contacted to an aqueous absorption solution. Selected compounds for absorption solutions are monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), methyldiethanolamine (MDEA) and 2-amino-2,hydroxymethyl-1,3-propanediol (Tris). Solutions were prepared at a concentration of 1.44x1 O'1 M.
Operating conditions were the following: gas flow rate is 1.0 g/min, absorption solution flow rate is 0.5 L/min. Height of packing is 25 cm. Operating pressure is 1.4 psig.
Performance of absorption solutions are shown in Figure 2. Performance is expressed as a relative CO2 transfer rate:
From Figure 2, it can be observed that carbonic anhydrase increased CO2 absorption for all solutions, except for the MEA solution. The absence of increase between the test with and without enzyme is due to the fact that the efficiency of the MEA solution was of 100% under these conditions. In this particular example, a relative transfer rate of 1 equals to 100% CO2 removal.
Example 4 A gas, containing 8% of CO2 (v/v) is fed to a packed bed reactor containing immobilized carbonic anhydrase. The solid substrate is a polymeric material. The gas is countercurrently contacted to an aqueous absorption solution. Selected compounds for absorption solutions are monoethanolamine (MEA) and 2-amino-2-methyl-1 -propanol (AMP). Solutions were prepared at a concentration of 87 mM.
Operating conditions were the following: gas flow rate is 3.0 g/min, absorption solution flow rate is 0.5 L/min. height of packing is 25 cm. Operating pressure is 1.4 psig.
Performance of absorption solutions are shown in Figure 3. Performance is expressed as a relative C02 transfer rate:
It can clearly be seen that carbonic anhydrase increases the absorption capacity of absorption solutions. This increase can be obtained both for amine-based chemical absorption solutions and physical solutions. Reduced costs with lower need for solvents could thus be obtained.
Although preferred embodiments of the present invention have been described in detail herein and illustrated in the accompanying drawings, it is to be understood that the invention is not limited to these precise embodiments and that various changes and modifications may be effected therein without departing from the scope or spirit of the present invention.
Claims (18)
- CLAIMS:1. A formulation for C02 reactions comprising: (a) a solution comprising: (i) water; and (ii) at least one tertiary amino reaction compound having the formula R3N and enabling reaction (A):(A); and (b) carbonic anhydrase to catalyze reaction (B):(B).
- 2. The formulation of claim 1, wherein the tertiary amino reaction compound R3N comprises a tertiary alkanolamine.
- 3. The formulation of claim 2, wherein the tertiary alkanolamine is selected from triethanolamine (TEA) and N-methyldiethanolamine (MDEA).
- 4. The formulation of claim 1, wherein the carbonic anhydrase is directly present in and flows with the solution, is immobilized on a support, or is immobilized on a packing.
- 5. A method for absorption of C02 comprising contacting gaseous C02 with an aqueous C02 absorption solution comprising at least one C02 absorption compound and carbonic anhydrase wherein the carbonic anhydrase enables at least a 80% increase in C02 transfer rate relative to the same aqueous C02 absorption solution without the carbonic anhydrase.
- 6. The method of claim 5, wherein the carbonic anhydrase is directly present in and flows with the aqueous C02 absorption solution, is immobilized on a support, or is immobilized on a packing.
- 7. A method to enhance C02 absorption, comprising providing carbonic anhydrase within a packed bed reactor; contacting gaseous C02 with an aqueous C02 absorption solution comprising at least one C02 absorption compound within the packed bed reactor in the presence of the carbonic anhydrase; and operating the packed bed reactor to enable increased C02 transfer rate of at least 80% relative to the same absorption solution without the carbonic anhydrase.
- 8. The method of claim 7, wherein the carbonic anhydrase is directly present in and flows with the aqueous C02 absorption solution, is immobilized on a support, or is immobilized on packing of the packed bed reactor.
- 9. A formulation for absorption of C02 comprising water and at least one C02 absorption compound comprising a carbonate salt, the water and the at least one C02 absorption compound forming an alkaline carbonate salt based solution; and carbonic anhydrase to enhance the absorption of C02 into the alkaline carbonate salt based solution.
- 10. The formulation of claim 9, wherein the carbonate salt comprises potassium carbonate or sodium carbonate.
- 11. The formulation of claim 9, wherein the carbonic anhydrase is directly present in and flows with the alkaline carbonate salt based solution, is immobilized on a support, or is immobilized on a packing.
- 12. A formulation for absorption of C02 comprising water, at least one aliphatic C02 absorption compound non-reactive directly with C02, and carbonic anhydrase to enhance the absorption of the C02 into the water.
- 13. The formulation of claim 12, wherein the C02 absorption compound comprises an alkanolamine.
- 14. The formulation of claim 13, wherein the alkanolamine comprises a tertiary alkanolamine.
- 15. The formulation of claim 12, wherein the carbonic anhydrase is directly present in and flows with the water, is immobilized on a support, or is immobilized on a packing.
- 16. A formulation for catalysis of the following reaction:comprising water, at least one reaction compound comprising a cation and an anion having a carboxylate function, the water and the at least one reaction compound forming a solution; and carbonic anhydrase to catalyze the reaction.
- 17. The formulation of claim 16, wherein the reaction compound comprising a cation and an anion having a carboxylate function is selected from bmim-acetate and hmim-acetate.
- 18. The method of claim 16, wherein the carbonic anhydrase is directly present in and flows with the solution, is immobilized on a support, or is immobilized on a packing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2013205811A AU2013205811B2 (en) | 2005-02-24 | 2013-05-10 | An improved CO2 absorption solution |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/655,466 | 2005-02-24 | ||
| AU2011201028A AU2011201028B2 (en) | 2005-02-24 | 2011-03-08 | An improved CO2 absorption solution |
| AU2013205811A AU2013205811B2 (en) | 2005-02-24 | 2013-05-10 | An improved CO2 absorption solution |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2011201028A Division AU2011201028B2 (en) | 2005-02-24 | 2011-03-08 | An improved CO2 absorption solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2013205811A1 AU2013205811A1 (en) | 2013-05-30 |
| AU2013205811B2 true AU2013205811B2 (en) | 2016-06-30 |
Family
ID=48483809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2013205811A Active AU2013205811B2 (en) | 2005-02-24 | 2013-05-10 | An improved CO2 absorption solution |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU2013205811B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030224504A1 (en) * | 2002-05-31 | 2003-12-04 | Jean-Sebastien Blais | Ventilation system for an enclosure in which people live and a method thereof |
-
2013
- 2013-05-10 AU AU2013205811A patent/AU2013205811B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030224504A1 (en) * | 2002-05-31 | 2003-12-04 | Jean-Sebastien Blais | Ventilation system for an enclosure in which people live and a method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2013205811A1 (en) | 2013-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2599493C (en) | An improved co2 absorption solution | |
| US10226733B2 (en) | Process for CO2 capture using carbonates and biocatalysts | |
| US10220348B2 (en) | Process for CO2 capture using micro-particles comprising biocatalysts | |
| RU2378039C2 (en) | Polyamine/alkaline salt mixture for removing carbon dioxide from gas streams | |
| Wang et al. | Amine-based absorbents selection for CO2 membrane vacuum regeneration technology by combined absorption–desorption analysis | |
| EP0875280A2 (en) | Method for removing carbon dioxide from combustion exhaust gas | |
| JP5506486B2 (en) | Aqueous solution that effectively absorbs and recovers carbon dioxide contained in gas | |
| JP2009006275A (en) | Efficient recovering method of carbon dioxide in exhaust gas | |
| US20140106440A1 (en) | Enhanced enzymatic co2 capture techniques according to solution pka, temperature and/or enzyme character | |
| KR20120067046A (en) | An absorbent for capturing carbon dioxide comprising amino acid having multi amine groups and metal hydroxide | |
| CN114570178A (en) | Carbon dioxide absorbent and preparation method and application thereof | |
| JP2017121610A (en) | Acidic gas absorbent, acidic gas removing method and acidic gas removing device | |
| Novitskii et al. | Optimization of methods for purification of gas mixtures to remove carbon dioxide (a review) | |
| KR20150021698A (en) | Compound including oxalate, carbon dioxide absorbent comprising the same, preparing method of the carbon dioxide absorbent and removing method of carbon dioxide | |
| AU2013205811B2 (en) | An improved CO2 absorption solution | |
| Fradette et al. | CO2 absorption solution | |
| WO2013159228A1 (en) | Co2 capture with carbonic anhydrase and tertiary amino solvents for enhanced flux ratio | |
| Fradette et al. | CO 2 absorption solution | |
| CN102898313B (en) | Azimino compound used for trapping acid gas, and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGA | Letters patent sealed or granted (standard patent) | ||
| PC | Assignment registered |
Owner name: SAIPEM S.P.A. Free format text: FORMER OWNER(S): CO2 SOLUTION INC. |