Patent Application
20220288531
The present disclosure relates generally to the field of Environmental Sciences and Technology. In particular, the present invention relates to a novel phase transfer solvent composition for enhanced CO2 and/or H2S capture from flue gas and biogas having various gaseous compositions. More specifically, the disclosure relates to improved enzymatic and solvent systems, which upon CO2/H2S capture forms selective phases with higher CO2/H2S loading efficiency and low regeneration energy over the existing solvent systems.
CO2 emission from post-combustion streams is the major anthropogenic source of greenhouse gas responsible for global climate change. With the ever-growing industrial demand of fossil fuel use, CO2 accumulation within the atmosphere is predicted to increase substantially. To reduce the impact of the CO2 emissions from multiple sources, capture of CO2 has been advocated.
Among the post combustion carbon capture technologies, chemical absorption using aqueous amine solutions with thermal regeneration of the solvent is the most developed and applied technology for CO2 capture. Most of the energy required for CO2capture in amine scrubbing systems is used for regenerating the solvent, which makes the amine scrubbing very cost intensive for their commercial application. The development of new solvents or solvent blends is an important way of reducing the energy demand in amine scrubbing plants.
New class of solvent systems known as phase transitional solvents (PTS), have attracted increased interest for their potential to substantially reduce both energy use and equipment costs for CO2 capture. These solvents are homogeneous (single-phase) solvents before CO2 is loaded and upon CO2 absorption or a temperature shift, they form multiple phases:
a CO2-enriched phase and a CO2-lean phase. Because only the CO2-enriched liquid phase is used for solvent regeneration, the mass of solvent that requires regeneration is decreased. Consequently, the heat required to heat the solvent (sensible heat) is reduced.
There are few CO2 absorption and desorption using phase transfer solvent have been disclosed in the prior art.
US20070237695A1 relates to a method and system for gas separation using a liquid absorbent absorbing one of the gases to be separated, where the absorbent spontaneously separates into a phase rich in the absorbed gas, and a phase lean in the absorbed gas. The active agent in the not identified but preferred agents is indicated to be selected from the group consisting of alkaline salts, ammonium, alkanolamines, amines, amides and combinations thereof.
WO2013000953A2 described a liquid, aqueous CO2 absorbent comprising two or more amine compounds, where the aqueous solution of amines having absorbed CO2 is not, or only partly miscible with an aqueous solution of amines not having absorbed CO2, where at least one of the amines is a tertiary amine, and where at least one of the amines is a primary and/or a secondary amine, wherein the tertiary amine is DEEA and the primary and/or secondary amine(s) is (are) selected from DAB, DAP, DiAP, DMPDA, HEP, or the tertiary amine is DIPAE, or N-TBDEA and primary and/or secondary amine(s) is (are) selected from DAB, DAP, DiAP, DMPDA, HEP, MAPA, and MEA, and a method for CO2 capture using the CO2 absorbent.
WO2010126694A1relates to a method for de-acidizing an acid gas mixture using an absorbent comprising an amine dissolved in a mixture at a first concentration. After absorption of the acid gas, the absorbent forms a concentrated-amine phase, this is separated from the remainder of the absorbent and is introduced into a regeneration unit, whereas the remaining of the absorbent is recycled back into the absorption unit. A series of organic solvents are mentioned as the solvent, together with water and aqueous solutions. Organic solvents are mentioned as preferred solvents. The only exemplified absorbents are MEA in isooctane, which spontaneously forms a concentrated amine phase containing MEA and the reaction product of MEA and CO2, and an aqueous carbonate solution, which forms insoluble bicarbonate on absorption of CO2.
WO2010044836A1 relates to a method for de-acidizing an acid gas mixture using an absorbent comprising a carrier phase and an organic phase that is immiscible with the carrier phase. Introduction of an organic solvent as described herein is unwanted, mixed solvent systems add complexity to the systems.
WO2017035667A1 The present description relates to recombinant or engineered carbonic anhydrase polypeptides, variants, and functional derivatives thereof, having improved properties that make them advantageous for use in CO2 capture operations (e.g., CO2 capture solvents, alkaline pH, and/or elevated temperatures), as well as polynucleotides and vectors encoding same. The present description also relates to methods, processes and systems for CO2capture which make use of the recombinant or engineered carbonic anhydrase polypeptides, variants, and functional derivatives thereof.
CA2827024A1 describes a carbonic anhydrase system and processes are disclosed. The system has a reaction chamber, liquid inlet, gas inlet, liquid outlet and gas outlet, and uses carbonic anhydrase on or in substrates in suspension in the liquid for catalyzing a reaction of CO2 into bicarbonate and hydrogen ions to obtain a treated gas and an ion-rich solution.
Ye et. al “Novel biphasic solvent with tunable phase separation for CO2 capture: Role of water content in mechanism, kinetics, and energy penalty.” Environmental science & technology 53, no. 8 (2019): 4470-4479 describes a phase transfer system composed of triethylenetetramine (TETA) and 2-(diethylamino) ethanol (DEEA) blends.
Pinto et.al “Evaluation of a phase change solvent for CO2 capture: Absorption and desorption tests.” International Journal of Greenhouse Gas Control 28 (2014): 318-327 describes a blend of a tertiary amine (DEEA) and a diamine (MAPA) for CO2 capture.
Jiang et.al, Environmental Science & Technology 54, no. 12 (2020): 7601-7610 describes a phase splitting agent-regulated biphasic solvent for efficient CO2 capture with a low heat duty.
The drawbacks of the above-said process are:
The present address the problem existing in the art by providing a novel phase transfer solvent composition for enhanced CO2 and/or H2S capture from flue gas and biogas having various gaseous compositions. More specifically, the disclosure relates to improved enzymatic and solvent systems, which upon CO2/H2S capture forms selective phases with higher CO2/H2S loading efficiency and low regeneration energy over the existing solvent systems. The disclosure further provides a phase transfer solvent composed of a primary amine/secondary amine, a tertiary amine, a hyperthermophilic enzyme, thermoregulatory enzyme stabilizer, phase splitting agent, phase stabilizing agent and thermo-conductive nanofluid, where the combination synergistically improves CO2/H2S loading and have a phase separation behaviour with energy-efficient regeneration for CO2/H2S.
Moreover, suitable combination of enzyme and solvent synergistically results in low corrosion, improved cyclic capacity and low viscosity alteration. The whole process is “stand alone” The possible advantages of the present inventions, but not limited to, are:
Objective:
An aim of the present invention is to provide a novel phase transfer solvent composition for enhanced CO2 and/or H2S capture from flue gas and biogas having various gaseous compositions.
Another objection of the present invention is to provide a process of preparing the phase transfer solvent composition of the present invention.
The invention provides a phase transfer solvent composed of a primary amine/secondary amine, a tertiary amine, a hyperthermophilic enzyme, thermoregulatory enzyme stabilizer, phase splitting agent, phase stabilizing agent and thermo-conductive fluid, where the combination synergistically improves CO2/H2S loading and exhibit a phase separation behavior with energy-efficient regeneration for CO2/H2S compared to conventional solvent systems. Further, the present invention provides a process of preparing the phase transfer solvent composition of the present invention.
These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings wherein:
For the purpose of promoting an understanding of the principles of the invention, reference will now be made to the embodiments illustrated in the figures and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated system, and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skilled in the art to which this invention belongs. The system, methods, and examples provided herein are illustrative only and not intended to be limiting.
The terminology and structure employed herein is for describing, teaching and illuminating some embodiments and their specific features and elements and does not limit, restrict or reduce the spirit and scope of the invention.
The invention discloses a novel phase transfer solvent composition for enhanced CO2 and/or H2S capture from flue gas and biogas having various gaseous compositions. More specifically, the disclosure relates to improved enzymatic and solvent systems, which upon CO2/H2S capture forms selective phases with higher CO2/H2S loading efficiency and low regeneration energy over the existing solvent systems. The disclosure further provides a phase transfer solvent composed of a primary amine/secondary amine, a tertiary amine, a hyperthermophilic enzyme, thermoregulatory enzyme stabilizer, phase splitting agent, phase stabilizing agent and thermo-conductive fluid, where the combination synergistically improves CO2/H2S loading and exhibit a phase separation behaviour with energy-efficient regeneration for CO2/H2S.
In an aspect of the present invention, inventors provide a phase transfer solvent composition for enhanced CO2 and/or H2S capture from flue gas and biogas having various gaseous compositions, comprising:
In an embodiment, said compound having minimum one primary and/or one secondary amine groups are selected from group consisting of Monoethanolamine, Diethanolamine, Triethanolamine, Monomethylethanolamine, 2-(2-aminoethoxy)ethanol, Aminoethylethanolamine, Ethylenediamine (EDA), Diethylenetriamine (DETA), Triethylenetetramine (TETA). Tetraethylenepentamine (TEPA), 2-amino 2methyl-1-proponal (AMP), 2-(ethyamino)-ethanol (EAE), 2-(methylamino)-ethanol (MAE), 2-(diethylamino)-ethanol (DEAE), diethanolamine (DEA), diisopropanolamine (DIPA), methylaminopropylamine (MAPA), 3-aminopropanol (AP), 2,2-dimethyl-1,3-propanediamine (DMPDA), 3-amino-1-cyclohexylaminopropane (ACHP), diglycola mine (DGA), 1-amino-2-propanol (MIPA), Isobutyl amine, 2-amino-2-methyl-ipropanol, 2-(2-aminoethylamino)ethanol, 2-amino-2-hydroxymethyl-i,3-propanediol, N-methyldiethanolamine, dimethylmonoethanolamine, diethylmonoethanolamine, triisopropanolamine and triethanolamine), trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamine, diethylmethylamine, diethylpropylamine, diethylbutylamine, N,N-diisopropylmethylamine, N-ethyldiisopropylamine, N,N-dimethyl ethyl amine, N,N-diethylbutylamine, 1,2-dimethylpropylamine, N,N-diethylmethylamine, N,N-dimethylisopropylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, N,N-dimethylbutylamine, N-methyl-1,3-diaminopropane, Piperazine and triethylenetetramine or a combination thereof.
In another embodiment, said compound having minimum one primary and/or one secondary amine groups has a concentration range of 20-50 wt % in phase transfer solvent and depend on the feed gas CO2 concentration.
In yet another embodiment, compounds having minimum one tertiary amine includes but not limited to diethylethanolamine, dimethylethanolamine, diisopropanolamine, methyldiethanolamine, triethanolamine, 2-Amino-2-MethylPropan-1-ol, bis (2-dimethylaminoethyl) ether, tetramethyl-1, 2-ethanediamine, tetramethyl-3-propane, N-methyl diethanolamine, Dimethylethanolamine Tetramethyl-6-hexanediamine , 1,3,5-Trimethylhexahydro-1,3,5-triazine N,N,N′,N′-Tetramethyl-2-butene-1,4-diamine, Pentamethyldipropylenetriamine, N,N-diethylethanolamine, N,N-dimethylbutylamine, 3-(methyloamino)propylamine, or a combination thereof.
In a further embodiment, compound having minimum one tertiary amine has a concentration range from 20-30 wt % in phase transfer solvent and depends on the feed gas CO2 concentration.
In an embodiment, said hyperthermophilic enzyme is Carbonic Anhydrase (CA) obtained from a source selected from the group consisting of Bacillus thermoleovorans IOC-S3 (MTCC 25023) and/or Pseudomonas fragi IOC S2 (MTCC 25025), and/or Bacillus stearothermophilus IOC S1 (MTCC 25030) and/or Arthrobacter sp. IOC-SC-2 (MTCC 25028).
In another embodiment, said hyperthermophilic enzyme has concentration range of 10-50 ppm of the total phase transfer solvent.
In yet another embodiment, said thermoregulatory enzyme stabilizer is in the concentration range of 2-4 ppm per 1000 U/mg of enzyme.
In a further embodiment, said phase splitting agent is selected from sulfolane, tetrahydrothiophene-1-oxide, butadiene sulfone, and a combination thereof.
In an embodiment, said phase splitting agent has a concentration range from 1-5% in phase transfer solvent and depends on the tertiary amine concentration.
In another embodiment, said phase stabilizing micellar agent is selected from the group consisting of N-[2-[(2-Aminoethyl) amino]ethyl]-9-octadecenamide (AMEO), n-Benzalkonium chloride (BAC), CnH(2n+1)—COO(CH2CH2O)12CH3, Polyoxythylene alkyl ether, n-Alkyltrimethyl ammonium surfactant, Potassium alkanoate, Dodecylpyridinium bromide, Octylglucoside, Sodium dodecyl sulfate, trans-Cinnamaldehyde, Sodium bis-(2-ethylhexyl)-sulfosuccinate, Cetylpyridinium chloride, Primary alcohol ethoxylate, Polyoxyethylene nonyl phenyl ether, Polyethylene glycol esters, Linoleate, dodecylamine or a combination thereof.
In yet another embodiment, said phase stabilizing micellar agent has a concentration range from 50-70 ppm in phase transfer solvent.
In a further embodiment, said thermo-conductive fluid comprises nano-fluids of SiO2, Al2O3, and TiO2, Al2O3, TiCl2/Nano-γ-Al2O3, CoFe2O4, magnetic Fe3O4, Ga2O3, functional silica, colloidal In2O3, ZnO, CoO, MnO2, Fe3O4, PbS, MFe2O4 (M=Fe, Co, Mn, Zn), Lewis acid ZrO2, silica boron sulfuric acid nanoparticles, Ni metal nanoparticles loaded on the acid-base bifunctional support (Al2O3), Co3O4 nanoparticles, oxide or metallic nano particle.
In an embodiment, said thermo-conductive fluid has a size in the range of between 10-50 nm and the concentration of the thermo-conductive fluid particle side ranges between 6-8 ppm.
In a second aspect of the present invention, the inventors provide a process of preparing the phase transfer solvent composition as claimed in claim 1, wherein said process comprises the steps of :
In an embodiment, said Step 1 comprises:
In another embodiment, said condition for isolation of hyperthermophilic enzyme is as follows:
wherein the extracted enzyme has concentration of 100-150 mg/ml with an p-NPA activity of 1800-2000 U/mg, able to be stored at −20° C. for two years without loss of activity, able to be stored at room temperature when immobilized can be stored for 1 year with 95-98% of initial activity and has a thermal stability of 100-110° C.
In yet another embodiment, the thermoregulatory enzyme stabilizer is prepared using metal complexation with selective oligonucleotide.
In a further embodiment, the oligonucleotide is a single stranded hexamer oligonucleotide with a minimum of two thiosine bases such as TTACTA, TTAATC, TTGATA, and TTGCTC or a combination thereof and the metal salt used for complexation is a chloride salt of Fe, Co, Cu and Ni or a combination thereof.
In an embodiment, the concentration of oligonucleotides and metal salts were of 5-10 pmol/μl and 50-100 pmol/μl, respectively for the synthesis of thermoregulatory enzyme stabilizer.
In another embodiment, complexation of thermoregulatory enzyme stabilizer and hyperthermophilic enzyme is due to hydrogen bonding.
In yet another embodiment, complexation of thermoregulatory enzyme stabilizer and hyperthermophilic enzyme is carried out by mixing 2 ppm of thermoregulatory enzyme stabilizer per 1000 U/mg of hyperthermophilic enzyme in presence of phosphate buffer (50 mM) of pH 6-6.5.
In a further embodiment, the activity of hyperthermophilic enzyme is enhanced after complexation with thermoregulatory enzyme stabilizer.
In an embodiment, complexation of thermoregulatory enzyme stabilizer and hyperthermophilic enzyme catalyses CO2 absorption within a temperature range of 0-40° C.
In another embodiment, complexation of thermoregulatory enzyme stabilizer and hyperthermophilic enzyme catalyses CO2 desorption in the temperature range of 50-110° C.
In yet another embodiment, the complexation of thermoregulatory enzyme stabilizer and hyperthermophilic enzyme can be used in free flow, fixed bed, rotating bed and any other configuration.
In a further embodiment, the complexation of thermoregulatory enzyme stabilizer and hyperthermophilic enzyme will be affective for phase transformation solvent, homogeneous solvent or any other form of solvent used for CO2 capture.
In an embodiment, said Step 2 comprises:
In another embodiment, said Step 3 comprises:
In yet another embodiment, the CO2 concentration ranges from 0.02% to 99% , preferably 0.02% to 90% in the source gas and the H2S concentration ranges from 0.001% to 5%.
In a further embodiment, the CO2/H2S phases differ in density, the rich phase is heavier than the CO2/H2S lean phase, allowing the phases to be separated by density, gravity or centrifugation apparatus.
In an embodiment, the separation of phases happens in 1-10 s for both CO2 and H2S gas feed.
In another embodiment, the CO2 and H2S rich phase is routed to different stripper column to selectively separate high pure H2S and CO2.
In yet another embodiment, the regeneration temperature ranges from 75° C. to 95° C.
In a further embodiment, CO2 sources are carbon dioxide-containing flue gas, process gas or gas from bio-methanation.
In an embodiment, the resulting gas is passed through the solvent medium through in any suitable device forming the fine dispersion of gas which result in an increase in contact area, said gas is sparged in micro-bubble or nano-bubble size.
In another embodiment, the pressure of CO2/H2S ranges from ambient to 10 bar and temperature ranges between 20-50° C.
The following examples and experiments are for illustrative purposes only and not intended to limit the scope of this disclosure.
Material and Methods:
The typical concentration of components used in phase transfer solvent of the present invention are given in the following table-1
1. Preparation of Modified Hyperthermophilic Enzyme
The hyperthermophilic enzyme was extracted from Bacillus stearothermophilus IOC S1 (MTCC 25030). Initially, the microbes were grown in media having composition (in g/l) 6.0 g of Na2HPO4, 3.0 g of KH2PO4, 1.0 g of NH4Cl, 0.5 g of NaCl, 0.014 g of CaCl2, 0.245 g of MgSO4.7H2O, 10 mg of thiamine hydrochloride and 10 g of starch, and with 1 mM IPTG at 55° C. and 6.5 pH.
Enzyme expression was induced by the addition of 0.5 mM ZnSO4 and the cells were grown overnight at 55° C. The cells were lysed by the use of a Bead-Beater and cell debris was removed by centrifugation. The pooled fractions containing the enzyme were dialyzed against 0.1 M Tris/SO4 at pH 7.5. The enzyme was extracted from the nutrient medium by ammonium sulfate precipitation method. The purity of the enzyme was monitored by SDS/PAGE by comparing it with commercially available enzyme. The concentration of extracted enzyme was found to be 145 mg/ml by UV-Vis assay with p-NPA activity of 1955 U/mg. The enzyme was stored at RT.
For the preparation of thermoregulatory enzyme stabilizer, oligonucleotid of sequence TTACTA was synthesized. Oligonucleotides (100 mM oligonucleobases) and Iron chloride (100 mM) were prepared in HEPES buffer (10 mM, 1 mM magnesium nitrate, and pH 7.2).
Oligonucleotides and Iron chloride were then mixed with equal volumes. The final concentration of both oligonucleobases and iron chloride were both 50 mM. After equilibration at 30° C. for 10 minutes, the stable Fe-oligonucleotides complex was obtained and confirmed by appearance of sharp ligand to metal charge transfer spectra at 622 nm. The complex was collected by centrifugation with an rpm 8000 for 10 min.
2 ppm of thermoregulatory enzyme stabilizer was added to isolated hyperthermophilic enzyme (1L) having an activity of activity of 1955 U/mg. The solution was placed in the shaker overnight at 120 rpm at 60° C. resulting the modified hyperthermophilic enzyme. The characteristic of modified hyperthermophilic enzyme is given in table-2 Comparison of the activity for hyperthermophilic enzyme and modified hyperthermophilic enzyme using CO2 or p-NPA as substrate is given in Table-2.
2. Preparation of Phase Transfer Solvent System
In a 2L flask 5M diethylethanolamine and N,N-Dimethyl-1,3-diaminopropane (2M) were mixed for 2 h. To the solution 0.2M sulfolane was added drop-wise with 2 ml/min with constant stirring. To the same solution 50 ppm of modified hyperthermophilic enzyme was inserted followed by 70 ppm of phase stabilizing micellar agent (Sodium dodecyl sulfate). After 2 h of constant stirring 8 ppm of thermo-conductive fluid (Fe2O4 having average particle side 24 nm) was inserted to obtain the final phase transfer solvent system. The mixture is homogeneous at Room temperature.
3. Evaluation of Novel Phase Transfer Solvent
A known volume and mass (500 ml) of the solvent was weighed into the reactor and a synthetic mixture of CO2 (35%) and balance N2) was inserted to the solution, with a flow of 20 ml/min, was bubbled into the solvent. After bubbling through the solution, the gas stream was cooled on-line through two condensers placed on top of each other and the condensate was directly returned to the reactor. The purified gas was collected for GC analysis. The CO2 loading was studied by gravimetric method under equilibrium condition. It was observed that upon CO2 loading, the CO2-rich phase formed in the bottom constitute 22% of the total solvent volume. The CO2 rich phase was separated after used for desorption tests in stripping column.
4. CO2 Loading Capacity in Rich and Lean Amine
Preparation of Phase Transfer Solvent
The phase transfer solvent was prepared based on the protocol mentioned step-1,2 and 3 of the example-1.
Biogas of composition (75% Methane, 5000 ppm H2S balance CO2) was used for the study. The flow rate of solvent was kept 20 ml/min, was bubbled into the solvent. After bubbling through the solution, the gas stream was cooled on-line through two condensers placed on top of each other and the condensate was directly returned to the reactor. The purified gas was collected for GC analysis. The CO2/H2S loading was studied by gravimetric method under equilibrium condition. It was observed that upon CO2 loading, the CO2-rich phase formed in the bottom constitute 21.5% of the total solvent volume, H2S rich phase was 7% of the total volume. The CO2 and H2S rich phase were separated after used for desorption tests in stripping column.
It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained, and since certain changes may be made in the constructions set forth without departing from the spirit and scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense. The invention has been described with reference to preferred and alternate embodiments. Modifications and alterations will become apparent to those skilled in the art upon reading and understanding the detailed discussion of the invention provided herein. This invention is intended to include all such modifications and alterations insofar as they come within the scope of the present invention. These and other modifications of the preferred embodiments as well as other embodiments of the invention will be obvious from the disclosure herein, whereby the foregoing descriptive matter is to be interpreted merely as illustrative of the invention and not as a limitation.
Finally, to the extent necessary to understand or complete the disclosure of the present invention, all publications, patents, and patent applications mentioned herein are expressly incorporated by reference therein to the same extent as though each were individually so incorporated.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202121009850 | Mar 2021 | IN | national |
